In-situ kerogen conversion and product upgrading

ABSTRACT

Disclosed herein are methods for extracting a kerogen-based product from subsurface (oil) shale formations. These methods rely on chemically modifying the shale-bound kerogen using a chemical oxidant so as to render it mobile. The oxidant is provided to a formation fluid in contact with the kerogen in the subsurface shale. A mobile kerogen-based product which includes the organic acids is withdrawn from the subsurface shale formation and processed to isolate the organic acids contained therein. The isolated organic acids are upgraded by a reaction process that make the products suitable as refinery feedstocks, fuel or lubricant blendstocks, reaction intermediates, chemical feedstocks, or chemical intermediate blendstocks.

RELATED APPLICATION

The subject application claims priority to U.S. Provisional ApplicationSer. No. 61/426,340, filed Dec. 22, 2010, the contents of which areincorporated herein by reference in their entirety.

BACKGROUND

This application is also related to U.S. Publication No. US2012-0160486;U.S. Publication No. US2012-0175114; U.S. Publication No.US2012-0175116, and U.S. Publication No. US2013-0161001, incorporatedherein by reference in their entirety. If proponents of Hubbert peaktheory are correct, world oil production will soon peak, if it has notdone so already. Regardless, world energy consumption continues to riseat a rate that outpaces new oil discoveries. As a result, alternativesources of energy must be developed, as well as new technologies formaximizing the production and efficient consumption of oil. See T. Mast,Over a Barrel: A Simple Guide to the Oil Shortage, Greenleaf Book Group,Austin, Tex., 2005.

A particularly attractive alternative source of energy is oil shale, theattractiveness stemming primarily from the fact that oil can be“extracted” from the shale and subsequently refined in a manner muchlike that of crude oil. Technologies involving the extraction, however,must be further developed before oil shale becomes a commercially-viablesource of energy. See J. T. Bartis et al, Oil Shale Development in theUnited States: Prospects and Policy Issues, RAND Corporation, Arlington,Va., 2005.

The largest known deposits of oil shale are found in the Green RiverFormation, which covers portions of Colorado, Utah, and Wyoming.Estimates on the amount of recoverable oil from the Green RiverFormation deposits are as high as 1.1 trillion barrels of oil—almostfour times the proven oil reserves of Saudi Arabia. At current U.S.consumption levels (˜20 million barrels per day), these shale depositscould sustain the U.S. for another 140 years (Bartis et al.) At the veryleast, such shale resources could moderate the price of oil and reduceU.S. dependence on foreign oil.

Oil shale typically consists of an inorganic component (primarilycarbonaceous material, i.e., a carbonate), an organic component(kerogen) that can only be mobilized by breaking the chemical bonds inthe kerogen, and frequently a second organic component (bitumen).Thermal treatment can be employed to break (i.e., “crack”) the kerogeninto hydrocarbon chains or fragments, which are gas or liquids underretort conditions, and facilitate separation from the inorganicmaterial. This thermal treatment of the kerogen is also known as“thermal upgrading” or “retorting,” and can be done at either thesurface or in situ, where in the latter case, the fluids so formed aresubsequently transported to the surface.

In some applications of surface retorting, the oil shale is first minedor excavated, and once at the surface, the oil shale is crushed and thenheated (retorted) to complete the process of transforming the oil shaleto a crude oil—sometimes referred to as “shale oil.” See, e.g., Shumanet al., U.S. Pat. No. 3,489,672. The crude oil is then shipped off to arefinery where it typically requires additional processing steps (beyondthat of traditional crude oil) prior to making finished products such asgasoline, lubricant, etc. Note that various chemical upgradingtreatments can also be performed on the shale prior to the retorting,See, e.g., So et al., U.S. Pat. No. 5,091,076.

A method for in situ retorting of carbonaceous deposits such as oilshale has been described in Kvapil et al., U.S. Pat. No. 4,162,808. Inthis method, shale is retorted in a series of rubblized in situ retortsusing combustion (in air) of carbonaceous material as a source of heat.

The Shell Oil Company has been developing new methods that useelectrical heating for the in situ upgrading of subsurface hydrocarbons,primarily in subsurface formations located approximately 200 miles (320km) west of Denver, Colo. See, e.g., Vinegar et al., U.S. Pat. No.7,121,342; and Berchenko et al., U.S. Pat. No. 6,991,032. In suchmethods, a heating element is lowered into a well and allowed to heatthe kerogen over a period of approximately four years, slowly converting(upgrading) it into oils and gases, which are then pumped to thesurface. To obtain even heating, 15 to 25 heating holes could be drilledper acre. Additionally, a ground-freezing technology to establish anunderground barrier around the perimeter of the extraction zone is alsoenvisioned to prevent groundwater from entering and the retortingproducts from leaving. While the establishment of “freeze walls” is anaccepted practice in civil engineering, its application to oil shalerecovery still has unknown environmental impacts. Additionally, theShell approach is recognized as an energy intensive process and requiresa long timeframe to establish production from the oil shale.

In view of the aforementioned limitations of the above methods, simplerand more cost-effective methods of extracting the kerogen from the shalewould be extremely useful.

SUMMARY OF THE INVENTION

The present invention is directed to a process for producing mobileproducts from the organic matter that occurs in subsurface oil shale.Among other factors, the process is based on the discovery that kerogenin oil shale can be made to react at temperatures below pyrolysistemperatures to produce mobile reaction products that can be removedfrom the subsurface shale formation, isolated from the mobile reactionproducts, and upgraded to produce useful products, such as refineryfeedstocks, fuel and lubricant blendstocks, reaction intermediates,chemicals and chemical intermediates, and the like.

Further to the invention is the discovery that the mobile reactionproducts that are produced during the kerogen conversion reactions areorganic acids. Accordingly, the process includes a step of upgrading atleast a portion of the organic acids. The process for increasing thevalue of a kerogen-based product from a subsurface shale formationcomprises: providing an oxidant to kerogen in subsurface shale at atemperature in the range from 0° C. to 200° C. and recovering a mobilekerogen-based product comprising organic acids therefrom; isolating atleast a portion of the organic acids from the mobile kerogen-basedproduct; and upgrading the isolated organic acids. In one embodiment,the process further comprises isolating at least a portion of theorganic acids from the mobile kerogen-based product by employing anprocess selected from the group consisting of pH titration, fractionalneutralization, esterification, extraction, distillation, membraneseparation, froth flotation, phase separation, electrostatic separation,filtering, centrifugal separation, coalescence, precipitation, thermalseparation, steam distillation, and any combination thereof, in anyorder.

In one embodiment, the process comprises isolating C₂₀+ organic acidsand C₂₀− organic acids from the mobile kerogen-based product, andcracking at least a portion of the C₂₀+ organic acids in a crackingprocess. In a further embodiment, C₂₀− hydrocarbon products from thecracking process are upgraded using a process selected from the groupconsisting hydroprocessing, hydrogenation, saturation, hydrotreating,hydrocracking, isomerization, fluid catalytic cracking, thermalcracking, esterification, oligomerization, reforming, alkylation,denitrification, desulfurization, and combinations thereof.

In another embodiment, the process comprises isolating C₃₅+ organicacids and C₃₅− organic acids from the mobile kerogen-based product, andcracking at least a portion of the C₃₅+ organic acids in a crackingprocess. The C₃₅− hydrocarbon products from the cracking process areupgraded using a process selected from the group consistinghydroprocessing, hydrogenation, saturation, hydrotreating,hydrocracking, isomerization, fluid catalytic cracking, thermalcracking, esterification, oligomerization, reforming, alkylation,denitrification, desulfurization, and combinations thereof.

In another embodiment, the process comprises: providing an oxidant tokerogen in subsurface shale; contacting the kerogen in the subsurfaceshale with the oxidant at a temperature in the range of between 0° C.and 200° C. to form organic acids; mobilizing at least a portion of theorganic acids from the subsurface shale to produce a mobilekerogen-based product; isolating C₃₅+ organic acids and C₃₅− organicacids from the mobile kerogen-based product; cracking the C₃₅+ organicacids in a first cracking step to form a first C₃₅− hydrocarbon productand unreacted C₃₅+ organic acids; treating the first C₃₅− hydrocarbonproduct in a process selected from the group consisting ofhydroprocessing, hydrogenation, saturation, hydrotreating,hydrocracking, isomerization, fluid catalytic cracking, thermalcracking, esterification, oligomerization, reforming, alkylation,denitrification, desulfurization, and combinations thereof, to form asecond C₃₅− hydrocarbon product; and recycling the unreacted C₃₅+organic acids to the first cracking step.

In a further embodiment, the first cracking step is selected from thegroup consisting of pyrolysis, partial oxidation, and fluid catalyticcracking and hydrocracking.

In a further embodiment, the process comprises treating a combination ofthe first C₃₅− hydrocarbon product and the C₃₅− organic acids in aprocess selected from the group consisting of hydroprocessing,hydrogenation, saturation, hydrotreating, hydrocracking, isomerization,fluid catalytic cracking, thermal cracking, esterification,oligomerization, reforming, alkylation, denitrification,desulfurization, and combinations thereof, to form a third C₃₅−hydrocarbon product.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block diagram illustrating an exemplary sequence of stepsinvolving the provision of a reactive fluid to a subsurface shaleformation that contains kerogen, the recovery of a mobile kerogen-basedproduct from the formation and the isolation of organic acid productsfrom the mobile kerogen-based product.

FIG. 2 is a block diagram illustrating the added step of passing anorganic extraction fluid to the mobile kerogen-based product forextracting at least a portion of the organic acids contained in themobile kerogen-based product.

FIG. 3 is a block diagram illustrating an exemplary sequence of stepsinvolving the provision of a reactive fluid to a subsurface shaleformation that contains kerogen, the further provision of an extractivefluid for mobilizing organic acids that are generated from kerogenreactions, the recovery of a mobile kerogen-based product from theformation and the isolation of organic acid products from the mobilekerogen-based product.

FIG. 4 illustrates carbon chain-size distribution of low molecularweight acids in kerogen permanganate oxidation products determined bygas chromatography/mass spectrometry.

FIG. 5 illustrates carbon chain-size distribution of hydrocarbonproducts formed by pyrolysis of high molecular weight organic acids inkerogen permanganate oxidation products determined by pyrolysis gaschromatography/mass spectrometry.

FIG. 6 illustrates an embodiment of the process for upgrading theorganic acids in the preparation of the organic acids as finishedproducts, as feedstocks or as blendstocks. Fig. further illustratesisolating organic acids from the product in which they are produced fromthe kerogen in the subsurface shale.

DETAILED DESCRIPTION OF THE INVENTION

Introduction

The present invention is directed to methods of extracting akerogen-based product from subsurface shale formation comprising kerogenin an inorganic matrix. The methods rely on chemically modifying theshale-bound kerogen to render it mobile using an oxidant that isprovided to the kerogen in the subsurface shale in a liquid medium. Theoxidant converts the kerogen to a mobile kerogen-based product attemperatures below that at which the kerogen thermally decomposes bypyrolysis or thermal cracking. The oxidant is maintained in thesubsurface shale formation for sufficient time to significantly reducethe oxidation activity of the oxidant. The present invention is alsodirected to systems for implementing such methods.

The process is for the conversion of carbonaceous deposits into mobileproducts, which may be recovered for use in the generation of energyand/or in the production of fuels, lubricants, solvents and/orpetrochemicals that are generally formed during petroleum processing andrefining. Any carbonaceous deposit may be beneficially treated by theprocess. Exemplary deposits include oil shale, coal, tar sands, heavyoil and the like. In the following description of the process, specificattention is paid to converting the hydrocarbonaceous material thatoccurs in what is commonly termed “oil shale”, with the understandingthat application of the process in its general form is not so limited.

DEFINITIONS

In accordance with this detailed description, the followingabbreviations and definitions apply. It must be noted that as usedherein, the singular forms “a”, “an”, and “the” include plural referentsunless the context clearly dictates otherwise. Thus, for example,reference to an “oxidant” includes a plurality of such.

As used herein, a range encompasses all values within the limits of thestated range, including the end members of the range. In an illustrativeexample, “having a pH in a range from 8 to 12” includes all integer andfractional values from 8 and 12, including a pH of 8 or a pH of 12.

As used herein, the terms “hydrocarbon” or “hydrocarbonaceous” or“petroleum” are used interchangeably to refer to material originatingfrom oil shale, coal, tar sands, crude oil, natural gas or biologicalprocesses. Carbon and hydrogen are major components of hydrocarbons;minor components, such as oxygen, sulfur and nitrogen may also occur insome hydrocarbons. The hydrocarbon fraction includes both aliphatic andaromatic components. The aliphatic component can further be divided intoacyclic alkanes, referred to as paraffins, and cycloalkanes, referred toas naphthenes. A paraffin refers to a non-cyclic, linear (normalparaffin) or branched (isoparaffin) saturated hydrocarbon. For example,a C₈ paraffin is a non-cyclic, linear or branched hydrocarbon having 8carbon atoms per molecule. Normal octane, methylheptane, dimethylhexane,and trimethylpentane are examples of C₈ paraffins. A paraffin-rich feedcomprises at least 10 wt %, at least 20 wt % or even at least 30 wt %paraffins. For example, a C₈ rich paraffinic feedstock contains at least10 wt. % C₈ hydrocarbons.

As disclosed herein, boiling point temperatures are based on the ASTMD-2887 standard test method for boiling range distribution of petroleumfractions by gas chromatography, unless otherwise indicated. Themid-boiling point is defined as the 50% by volume boiling temperature,based on an ASTM D-2887 simulated distillation.

As disclosed herein, carbon number values (i.e., C₅, C₆, C₈, C₉ and thelike) generally refers to a number of carbon atoms within a molecule.Carbon number ranges as disclosed herein (e.g., C₈ to C₁₂) refer tomolecules having a carbon number within the indicated range (e.g.,between 8 carbon and 12 carbon atoms), including the end members of therange. Likewise, an open ended carbon number range (e.g., C₃₅+) refersto molecules having a carbon number within the indicated range (e.g., 35or more carbon atoms), including the end member of the range. Asdescribed herein, carbon number distributions are determined by trueboiling point distribution and gas liquid chromatography.

Unless otherwise specified, feed rate to a catalytic reaction zone isreported as the volume of feed per volume of catalyst per hour. Ineffect, the feed rate as disclosed herein, referred to as liquid hourlyspace velocity (LHSV), is reported in reciprocal hours (i.e., hr⁻¹).

As used herein, the value for octane refers to the research octanenumber (RON), as determined by ASTM D2699.

The term “surface facility” as used herein is any structure, device,means, service, resource or feature that occurs, exists, takes place oris supported on the surface of the earth. The kerogen products that aregenerated in the process disclosed herein are recovered in surfacefacilities and upgraded or transported for upgrading.

“Shale,” as defined herein, generally refers to “oil shale” and is ageneral term applied to a group of rocks rich enough in organic material(called kerogen) to yield petroleum upon pyrolysis and distillation.Such shale is generally subsurface and comprises an inorganic (usuallycarbonate) component or matrix in addition to the kerogen component.

A “subsurface shale formation,” as defined herein, is an undergroundgeological formation comprising (oil) shale. The subsurface shaleformation comprises kerogen in an inorganic matrix.

A “low-permeability hydrocarbon-bearing formation,” as defined herein,refers to formations having a permeability of less than about 10millidarcies, wherein the formations comprise hydrocarbonaceousmaterial. Examples of such formations include, but are not limited to,diatomite, coal, tight shales, tight sandstones, tight carbonates, andthe like.

“Kerogen,” as defined herein and as mentioned above, is an organiccomponent of shale. On a molecular level, kerogen comprises very highmolecular weight molecules that are generally insoluble by virtue oftheir high molecular weight and likely bonding to the inorganiccomponent or matrix of the shale. In a geologic sense, kerogen is aprecursor to crude oil. Kerogen is typically identified as being one offive types: Type I, Type II, Type II-sulfur, Type III, or Type IV, basedon its C:H:O ratio and sulfur content, the various types generally beingderived from different sources of ancient biological matter.

“Kerogen-based,” and “kerogen-derived are terms used herein to denote amolecular product or intermediate derived from kerogen, such derivationrequiring a chemical modification of the kerogen, and the term beingexclusive of derivations carried out over geologic timescales.

“Extractible organics” are organic components of the subsurface shaleformation that are at least partially soluble in an organic solvent. Incontrast, the kerogen is not soluble in organic solvent. This organiccomponent that is at least partially soluble is referred to herein as“extractible organics”. This extractible organic component includes whatis commonly referred to as “bitumen”. The extractable organic componentis a solid or semi-solid material that is soluble or at least partiallysoluble in an organic solvent. As such, the extractable organiccomponent can be removed by extraction using an organic solvent.Extraction of the extractable organic component makes the kerogen moreaccessible. In the present methods, extraction of the extractableorganic component makes the kerogen more accessible to oxidants forreaction to create mobile kerogen-based product. Extraction of theextractable organic component is disclosed in U.S. application Ser. No.13/335,195, “Preconditioning a Subsurface Shale Formation by RemovingExtractable Organics”, filed Dec. 22, 2011, the contents of which areincorporated herein by reference in their entirety.

“Organic acid” is a term used herein to denote a molecular entitycontaining at least one carboxylic acid functional group, either in thenon-ionized form (e.g., —COOH), in the ionized form (e.g., —COO—), orsalts thereof. The term “organic acid” is meant to encompass a highmolecular weight kerogen fragment (e.g., a molecular mass of up to12,000 to 15,000 daltons and higher) comprising at least one carboxylicacid functional group. The term “organic acid” is further meant toencompass a low molecular weight acid, including a monoacid such asacetic acid and a diacid such as oxalic acid. As used herein, the term“monoacid” is used to denote having one carboxylic acid functional groupper molecule. Likewise, the term “diacid” denotes two, and “triacid”denotes three carboxylic acid functional groups per molecule.

The term “reactive fluid,” as used herein, refers to fluid comprising anoxidant that is passed to the kerogen in the subsurface shale formation.

The term “extractive fluid,” as used herein, refers to a fluid that isprepared with additives for mobilizing the organic acid reactionproducts in the subsurface shale.

The term “aqueous fluid” as used herein refers to any water containingfluid, including pure water, such as, municipal water; surface water,including from a lake, sea, ocean, river, and/or stream; formationwater; water associated with industrial activity; or mixtures thereof.

The term “formation water” as used herein refers to the water or aqueousfluid that is naturally occurring in a geological formation, such as thesubsurface shale formation, or in a subsurface aquifer. The amount (orpresence) of formation water in the formation, and the amount (orpresence) of formation water in contact with the kerogen in theformation, depends on a number of factors, including the depth of thesubsurface shale formation or the kerogen deposit located therein. Insome cases, formation water is present in the formation prior to thestart of the process for extracting a kerogen-based product from asubsurface shale formation. The naturally occurring formation water maycontain dissolved alkali materials from naturally occurring deposits inthe environment of the subsurface shale.

The term “formation fluid” as used herein, is the fluid in contact withthe kerogen in the subsurface shale formation. Formation fluid mayinclude the formation water that occurs naturally at, or in theenvironment of, the subsurface shale. Formation fluid may also include,for example, a fluid (or fluids) that are supplied to the kerogen fromthe surface. Formation fluid may also include, for example, oxidants, orsurfactants, or alkali materials, or mixtures thereof that are suppliedfrom the surface. Formation fluid may also include reaction productsfrom chemical reactions and/or physical absorption processes of thekerogen (and/or bitumen) in the subsurface shale formation.

The term “spent formation fluid,” as used herein, refers to theoxidation activity of the formation fluid, and by extension theconcentration of oxidant in the formation fluid. A spent formation fluidhas a reduced amount of oxidant, and therefore a reduced oxidationactivity toward the conversion of kerogen or products from kerogenconversion. Unless otherwise indicated, a spent formation fluid is onewhich produces an insignificant amount of reaction products at thetemperature of the fluid over the time in which the fluid is withdrawnas a mobile kerogen-based product from the formation.

The terms “natural” or “naturally occurring” refer to conditionsexisting before, or without, human intervention. Thus, a “naturalformation temperature,” as used herein, refers to the temperature of thesubsurface shale formation, prior to or in the absence of humanintervention with or in the formation. In a specific example, anaturally occurring aqueous fluid may originate from a subterraneanaquifer or from a surface body of water, such as a river or stream orfrom a pond or lake, and that has not been modified by man. In anotherspecific example, a “naturally occurring” aqueous basic solution refersto a solution present in the formation prior to, or in the absence of,human intervention in the formation.

A “surfactant” as used herein refers to any substance that reducessurface tension of a liquid, or reduces interfacial tension between twoliquids, or between a liquid and a solid, or facilitates the dispersionof an organic material into an aqueous solution.

The term “basic solution,” as used herein, refers to an aqueous solutionhaving a pH of greater than 7.

The term “acidic solution,” as used herein, refers to an aqueoussolution having a pH of less than 7.

A “dense phase fluid,” as defined herein, is a non-gaseous fluid. Suchdense phase fluids include liquids, supercritical fluids (SCFs), andfluids at supercritical conditions. The dense phase fluid can be anysuch fluid that suitably provides for increased accessibility of thekerogen to a fluid—typically due to fracturing and/or rubblizing of theshale in which the kerogen resides.

A “supercritical fluid,” as used herein, is any substance at atemperature and pressure above its thermodynamic critical point.Supercritical fluids can be regarded as “hybrid solvents” withproperties between those of gases and liquids, i.e., a solvent with alow viscosity, high diffusion rates and no surface tension. Commonsupercritical fluids include supercritical carbon dioxide (CO₂) andsupercritical water. For example, the critical temperature of CO₂ is31.1° C., and the critical pressure of CO₂ is 72.9 atm (7.39 MPa).

The term “mechanical stress,” as used herein, refers to structuralstresses within the shale formation that result from pressure variationswithin the formation. Such stress can lead to fracturing and/orrubblization of the shale formation.

The term “thermal stress,” as used herein, refers to structural stresseswithin the shale formation that result from thermal variations. Suchthermal stresses can induce internal mechanical stresses as a result ofdifferences in thermal coefficients of expansion among the variouscomponents of the shale formation. Like mechanical stress mentionedabove, thermal stress can also lead to fracturing and/or rubblization ofthe shale formation.

The term “fracturing,” as used herein, refers to the structuraldegradation of a subsurface shale formation as a result of appliedthermal and/or mechanical stress. Such structural degradation generallyenhances the permeability of the shale to fluids and increases theaccessibility of the kerogen component to such fluids. The term“rubblization,” as used herein, is a more extensive fracturing processyielding fracture planes in multiple directions that generate shalederived “rubble.”

The term “cracking,” as mentioned in the background section and as usedherein, refers to the breaking of carbon-carbon bonds in the kerogen soas to yield species of lower molecular weight. “Retorting,” providesthermal cracking of the kerogen. “Upgrading,” provides cracking of thekerogen, but can involve a thermal or chemical upgrading agent.Accordingly, the term “thermal upgrading” is synonymous with the term“retorting.”

Hydrocracking is a chemical reaction of liquid feed materials, includinghydrocarbons, petroleum and other biologically derived material, in thepresence of hydrogen and one or more catalysts, resulting in productmolecules having reduced molecular weight relative to that of the liquidfeed materials. Additional reactions, including olefin and aromaticsaturation and heteroatom (including oxygen, nitrogen, sulfur andhalogen) removal may also occur during hydrocracking.

Pyrolysis temperature, as used herein, is the temperature at which thekerogen thermally decomposes without the intervention of a catalytic orchemical agent.

The term “in situ,” as used herein refers to the environment of thesubsurface shale formation.

The term “commercial petroleum-based products,” as used herein, refersto commercial products that include, but are not limited to, gasoline,aviation fuel, diesel, lubricants, petrochemicals, and the like. Suchproducts can also include common chemical intermediates and/or blendingfeedstocks.

“Optional” or “optionally” means that the subsequently described eventor circumstance may, but need not, occur, and that the descriptionincludes instances where the event or circumstance occurs and instancesin which it does not.

Method Overview

The present invention is generally directed to methods for extracting akerogen-based product from a subsurface shale formation comprisingsubsurface shale. The methods include the steps of: providing an oxidantto kerogen in subsurface shale; contacting the kerogen in the subsurfaceshale with the oxidant at a temperature in the range from 0° C. and 200°C. to form organic acids; and mobilizing at least a portion of theorganic acids from the subsurface shale to produce a mobilekerogen-based product.

The step of contacting the kerogen with an oxidant generally involves anin situ chemical modification of the kerogen (e.g., cracking) and/orsurrounding shale so as to render the modified kerogen component mobile.Such chemical modification generally involves the making and/or breakingof chemical bonds. In one embodiment, the chemical modification involvesthe formation of reaction products that contain organic acid and/ororganic acid functional groups. At least a portion of these reactionproducts may be mobilized using an alkaline aqueous solution. The stepof transporting the mobile kerogen-based product out of the subsurfaceshale formation can generally be described as a means of flowing themobile kerogen-based product out of the subsurface formation, where sucha means can be active (e.g., pumping) and/or passive.

In an embodiment, the step of isolating the organic acids from themobile kerogen-based product involves reducing the relative solubilityof the organic acids in the mobile kerogen-based product. One exemplarymethod involves converting an ionized form of the acid, e.g., a salt ofthe acid such as a sodium salt, to the corresponding protonated (e.g.,non-ionized) form of the acid. In another embodiment, reducing therelative solubility involves contacting the mobile kerogen-based productwith a hydrocarbonaceous extractant for extracting at least some of theorganic acids from the mobile kerogen-based product to thehydrocarbonaceous extractant. In another embodiment, reducing therelative solubility involves converting the acid to a correspondingester. In an embodiments, the step of isolating the soluble organicacids involves separating the acids from a carrier fluid by physicalmeans, such as, for example, liquid-liquid separation, distillation,membrane separation, froth flotation, phase separation, electrostaticseparation, coalescence, biological processes, thermal separationprocesses, and steam distillation.

In one embodiment, the above-described method may involve one or moreadditional steps which serve to sample and subsequently analyze theshale prior to, or in the alternative during, or in the alternativeafter, performing the step of increasing the accessibility of thekerogen. Such sampling and analysis can have a direct bearing on thetechniques employed in the subsequent steps.

In one embodiment, the extracted kerogen-based product is upgraded(thermally and/or chemically) in a surface facility. Such surfaceupgrading can be intermediate to subsequent refining.

In an illustrative embodiment, a reactive fluid containing at least onereactive component and having a pH of at least 7 is provided to thekerogen in the subsurface shale. The reactive component facilitatescracking reactions in the kerogen, producing mobile organic acidreaction products. The mobile reaction products are absorbed into anaqueous fluid to form a mobile kerogen-based product; the reactionproduct enriched aqueous fluid is then removed to surface facilities forprocessing. A reactive fluid may further be provided to the subsurfaceshale for dissolving or otherwise absorbing mobile reaction products forremoval to surface facilities for processing. In another illustrativeembodiment, the reactive fluid containing at least one reactivecomponent, and having a pH of less than or equal to 7 is provided to thekerogen in the subsurface shale.

The subsurface shale formation comprises an organic component, at leasta portion of which is the kerogen as defined herein. The subsurfaceshale formation further comprises an inorganic component in addition tothe kerogen.

The subsurface shale formation is accessed from the surface through atleast one well. In general, the well will be cased, at least for aportion of its distance. Specifications for drilling access wells into asubsurface shale formation are known. In most applications of theinvention, multiple wells will be provided into the subsurface shaleformation, the well pattern based on recognized principles for thisapplication. In one embodiment, a portion of the wells are employed asinjection wells for passing fluids from the surface to the formation,and a portion of the wells are employed as production wells forwithdrawing fluids from the formation to the surface. Each of themultiple wells may be used successively as an injection well and aproduction well, depending on the needs of the process. In analternative, each well may be prepared and managed optimally as eitheran injection well or a production well. Specifications of each well forpreparing and using the well as an injection well and/or a productionwell can readily be developed by one of skill in the art.

Conversion Process

The conversion process is a chemical conversion process, with reagentsbeing provided to the kerogen to facilitate the fracture of chemicalbonds in the kerogen and between the kerogen and the inorganic matrix inwhich the kerogen naturally occurs. While the reagents that are providedto convert the shale may be provided as solids, liquids or gases, it hasbeen found that the conversion reactions are facilitated by theintroduction of liquid phase materials, or alternatively by using liquidphase materials that are naturally present in the shale formation, forconverting the kerogen. Use of liquid phase oxidants during kerogencracking conversion may advantageously be conducted at liquid phasetemperatures, including temperatures in the range from 0° C. to 200° C.The kerogen cracking conversion may advantageously be conducted atformation pressure, or at a pressure sufficiently above formationpressure to permit provision of liquid phase reactants to the kerogen inthe oil shale formation.

In one embodiment, the process includes providing an oxidant to kerogenin subsurface shale. Depending on the oxidant, it may be provided insolid, liquid or gaseous form. In liquid form, the oxidant may beprovided in acidic, neutral, or alkaline conditions; the choice of pHdepends at least in part on the type of oxidant used. Some oxidants arebetter suited for acidic conditions. For oxidants of this type, theoxidant is provided to the kerogen at a pH in a range from 1.5 to 6.5.Maintaining the pH in this range will generally require the addition ofan acidic material to the kerogen. Examples include mineral acids suchas hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid andcombination Examples s thereof, or organic acids such as one or more ofthe carboxylic acids having from 2 to 15 carbon atoms, or mixturethereof may be used. With the carboxylic acids, monoacids, diacids, ortriacids may be used. In one embodiment, the pH is maintained in a rangefrom 1.5 to 6.5 by provision of CO₂ to the kerogen, alone or incombination with other acids.

Some oxidants are better suited for conditions at neutral pH. Supplyingoxidants of this type generally involves supplying the oxidants incombination with a buffered solution, to maintain the pH in the neutralrange while contacting the mineral matter within the subsurface shale.

Some oxidants are better suited for alkaline conditions. For oxidants ofthis type, the oxidant is provided to the kerogen at a pH in a rangefrom 7 to 14, with an embodiment in the range from 7 to 9. Maintainingthe pH in the desired alkaline range will be facilitated in somesituations by the carbonate and bicarbonate materials that are naturalto the subsurface shale formation. Otherwise, the pH in the range from 7to 14, or in the range from 7 to 9, may be maintained by supply of analkaline material, such as a carbonate, a bicarbonate, an oxide, ahydroxide, or combinations thereof. In one embodiment, the pH ismaintained in a range from 7 to 9 by provision of CO₂ to the kerogen.

In one embodiment, the oxidant is provided to the kerogen in combinationwith a carrier fluid, the combination being prepared in surfacefacilities and passed to the subsurface shale through an injection well.Exemplary carrier fluids include an aqueous fluid, an ethanol fluid orcombinations thereof. An ethanol fluid contains ethanol, and typicallyat least 30 wt. % ethanol, such as from 30 wt. % to 100 wt. % ethanol.The ethanol fluid may also contain water. Likewise, the aqueous fluidmay contain ethanol. In one embodiment, the carrier fluid encompasses aconcentration range from 100 wt. % water to 100 wt. % ethanol, or anycombination between.

The carrier fluid generally contains sufficient oxidant to facilitatethe production of organic acids from the kerogen in a desired timeframe. Higher concentrations of the oxidant generally results in fasterreaction rates. In one embodiment, the carrier fluid contains from 0.1wt. % to 40 wt. % of the oxidant; in another embodiments from 0.1 wt. %to 25 wt. %; in another embodiment from 1 wt. % to 15 wt. %.

The carrier fluid is prepared at a pH that is suited for the particularoxidant used. In one embodiment, the carrier fluid has a pH in the rangefrom 7 to 14; in another embodiment in the range from 7 to 9; in anotherembodiment in the range from 1.5 to 6.5. Alkaline materials, inorganicacids, organic acids and CO₂ are suitable reagents for the preparationof the carrier fluid at different pH levels.

In one embodiment, the carrier fluid comprises an organic solvent.Illustrative organic solvents that are suitable include refinery streamsboiling in the range from 100° C. to 500° C.; C₄ to C₂₁ hydrocarbons,including naphtha, diesel fuel, and gas oils; alcohols, includingmethanol, ethanol, propanol, butanol; aromatics, including benzene,toluene, the xylenes and alkyl substituted variations thereof; ethers;ketones; esters; tetralin; n-methyl-2-pyrrolidone; tetrahydrofuran; and2-methyl-tetrahydrofuran. In one embodiment, the formation fluidincludes a mixture of an aqueous solvent and an organic solvent, in anyproportion.

Oxidant

The process comprises providing an oxidant to kerogen in subsurfaceshale. The oxidant is selected to be sufficiently stable to be deliveredto the kerogen, while maintaining sufficient oxidation activity tofacilitate the production of mobile reaction products when in contactwith kerogen in the subsurface shale. In one embodiment, the oxidant isselected to be environmentally benign. In one embodiment, the oxidant isselected to minimally impact aqueous aquifers in the region of thekerogen in the subsurface shale. The oxidant may be a single oxidant oran oxidant blend. In one embodiment, the oxidant is selected to bestable in an aqueous fluid which has been prepared to extract, absorb,dissolve or otherwise remove mobile reaction products from the kerogenin the subsurface shale. In one embodiment, the oxidant is selected toreact with kerogen to produce a mobile reaction product which contains ahigh amount (e.g., at least 10 wt. %) of organic acids in the C₃₅+range.

Exemplary oxidants include Oxone, Oxone combined with one or moremanganese porphyrin catalysts, Peracetic Acid, Hydrogen Peroxide,Fenton's reagent, Benzoyl Peroxide, Potassium Permanganate, andcombinations thereof.

Oxone is a trade name for potassium peroxymonosulfate (KHSO₅). Oxone iseffective as an oxidant for the conversion of kerogen, either alone orin combination with one or more manganese porphyrin catalysts. Theseoxidants tend to be more stable in acidic solution during long termstorage or handling. In one embodiment, oxone or an oxone blend isprovided to the kerogen at a pH in the range from 1.5 to 6.5, or in therange from 2.0 to 6.0. When supplying oxone to the kerogen in a basic(i.e., pH>7) solution, care is taken to reduce the natural decompositionof the oxidant. In one embodiment, oxone is provided to the incombination with an oxidation inhibitor, to inhibit the prematuredecomposition of the oxidant. In one embodiment, oxone is maintained inbasic solution in contact with kerogen for the minimum time required toconvert kerogen.

Peracetic acid, also known as peroxyacetic acid (CH₃CO₃H), is formed byreacting acetic acid with hydrogen peroxide. It is acidic as prepared,and will generally be provided to the kerogen in acidic solution. In oneembodiment, the peracetic acid is provided to the kerogen at a pH in therange from 1.5 to 6.5, or in the range from 2.0 to 6.0.

Hydrogen peroxide (H₂O₂) is typically stable in both acidic and basicsolution media. In one embodiment, hydrogen peroxide is provided to thekerogen in pure form, or combined with an amount of inhibitor to preventpremature decomposition of the hydrogen peroxide before contact withkerogen. In one embodiment, the hydrogen peroxide is provided to thekerogen at a pH in the range from 7 to 14; or in the range from 7 to 9.In one embodiment, the hydrogen peroxide is provided to the kerogen at apH of less than 7; or in the range from 1.5 to 6.5; or in the range from2.0 to 6.0.

Fenton's reagent is a combination of hydrogen peroxide with an iron(Fe₂+) catalyst. Fenton's reagent may be provided to the kerogen in bothacid and alkaline media. In one embodiment, the Fenton's reagent isprovided to the kerogen at a pH in the range from 7 to 14; or in therange from 7 to 9. In one embodiment, the Fenton's reagent is providedto the kerogen at a pH of less than 7; or in the range from 1.5 to 6.5;or in the range from 2.0 to 6.0.

Benzoyl peroxide ([C₆H₅C(O)]₂O₂) is minimally soluble in aqueoussolution; this oxidant is supplied to the kerogen in either an organicreactive fluid or as a slurry in an aqueous fluid. The slurry may beformed by directly slurrying the benzoyl peroxide into the aqueousfluid; or the benzoyl peroxide is first dissolved in an organic solventand the solution used to form the slurry.

In one embodiment, the process comprises providing a permanganateoxidant to the kerogen. Permanganate salts that are suitable for theprocess are readily soluble in aqueous solution, and are stable in basicsolutions. This oxidant is effective for producing high amounts ofdesirable high molecular weight kerogen fragments from kerogenconversion. In one embodiment, the permanganate is provided to thekerogen at a pH in the range from 7 to 14; or in the range from 7 to 9.In one embodiment, the permanganate is provided to the kerogen at a pHof less than 7; or in the range from 1.5 to 6.5; or in the range from2.0 to 6.0. The permanganate may be any soluble permanganate-containingmaterial. Ammonium permanganate, NH₄MnO₄; calcium permanganate,Ca(MnO₄)₂; potassium permanganate, KMnO₄; and sodium permanganate,NaMnO₄ are suitable permanganates for the process.

Surfactants

In one embodiment, a surfactant or mixture of surfactants are providedto the kerogen in the subsurface shale. The surfactant can be anysubstance that reduces surface tension of the fluid, or reducesinterfacial tension between two liquids, or one liquid and thesurrounding formation. The surfactant can also be chosen, for example,to increase the accessibility of the fluid to the kerogen, and/or toincrease the mobility of the reaction products from the kerogen, and/orto increase the effectiveness of the fluid for absorbing the reactionproducts. Suitable surfactants for use in the present fluids may beselected from nonionic, anionic or amphoteric surfactants.

Reactive Fluid

In one embodiment, the oxidant is combined with a solvent or carrierfluid to form a reactive fluid for passing to the kerogen in thesubsurface shale formation. The reactive fluid is designed andformulated to provide oxidant to the formation fluid, and to maintainthe integrity of the oxidant until it is in contact with the kerogen. Inone embodiment, the reactive fluid is further formulated to mobilizeorganic acids, which are formed during kerogen conversion, either as asuspension of colloidal kerogen fragments or as a solution of dissolvedorganic acids.

In one embodiment, the reactive fluid includes an aqueous solvent, or anorganic solvent, or combinations thereof.

In one embodiment, at least a portion of the reactive fluid is preparedin surface facilities. It may be desirable to locate the preparation ofthe aqueous reactive fluid such that the prepared fluid is conducted bypipeline transport from the preparation location to the injection wellfor providing the fluid to the subsurface shale.

The carrier from which the reactive fluid is prepared may be providedfrom any suitable source, such as, for example, one or more of municipalwater; surface water or water from a subsurface aquifer; bitter watersources with high pH levels, and containing quantities of one or more ofcarbonates, bicarbonates, oxides, and hydroxides, which are recoveredfrom subsurface aquifers; reactive water; and recycle aqueous fluidsfrom the kerogen conversion and extraction process. In one embodiment,the recycle aqueous fluid contains organic acids which remain insolution following the step of isolating at least a portion of theorganic acids from the mobile kerogen-based product. In one embodiment,the recycle aqueous fluid contains organic acids from the isolating stepthat are added back to the recycle aqueous fluid as surfactants. In onesuch embodiment, the recycle aqueous fluid contains at least 0.1 wt. %organic acids, including, for example, at least 0.5 wt. % organic acids;or at least 1.0 wt. % organic acids.

The oxidant concentration in the reactive fluid is determined by anumber of factors, including the stability and reactivity of the oxidantat the conditions of the subsurface formation, the nature of theinorganic component of the subsurface shale, and the desired productsfrom the kerogen conversion reactions. In one embodiment, the oxidantconcentration in the reactive fluid is kept at a low level to reduce thesecondary oxidation reactions of the organic acids which have beenliberated from the kerogen. In one embodiment, the reactive fluid asprovided to the subsurface shale formation contains in the range from0.1 wt. % to 100 wt. % oxidant; or in the range from 0.1 wt. % to 40 wt.% oxidant; or in the range of 0.1 wt. % to 25 wt. % oxidant, or in therange from 1 wt. % to 15 wt. %. In one embodiment, the reactive fluidcontains from 0.1 wt. % to 40 wt. % of the oxidant in a carrier fluidselected from the group consisting of an aqueous fluid, an ethanol fluidor combinations thereof.

The pH of the reactive fluid is tailored to the particular oxidant. Inone embodiment, the reactive fluid has a pH in a range from 7 to 14; inone embodiment, from 7 to 9. In one embodiment, the reactive fluid has apH in the range from 1.5 to 7; in one embodiment from 1.5 to 6.5.

In one embodiment, the desired reactive solution pH is achieved with theaddition of an acidic material to the reactive solution. Mineral acids,such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acidor organic acids such as one or more of the carboxylic acids having from2 to 15 carbon atoms, or mixture thereof may be used. With thecarboxylic acids, monoacids, diacids, or triacids may be used.

In one embodiment, the desired reactive solution pH is achieved with theaddition of an alkaline material to the reactive solution. Exemplaryalkaline materials which are useful include, for example at least onealkaline material selected from carbonates, bicarbonates, oxides, andhydroxides of, for example, sodium, potassium, calcium, and magnesium.An illustrative reactive fluid contains a molar ratio of carbonate tobicarbonate in the range from 5:95 to 95:5; or in the range from 10:90to 90:10; or in the range from 25:75 to 75:25.

In one embodiment, the reactive fluid comprises a surfactant or mixtureof surfactants for provision to the kerogen in the subsurface shale. Thesurfactant can be any substance that reduces surface tension of thefluid, or reduces interfacial tension between two liquids, or one liquidand the surrounding formation. The surfactant can also be chosen, forexample, to increase the accessibility of the fluid to the kerogen,and/or to increase the mobility of the reaction products from thekerogen, and/or to increase the effectiveness of the fluid for absorbingthe reaction products. Suitable surfactants for use in the presentfluids may be selected from nonionic, anionic or amphoteric surfactants.

In one embodiment, the reactive fluid further comprises at least onephase transfer catalyst to enhance the chemical interaction betweenkerogen and oxidant, for increasing the reaction rate of the oxidant. Inone such embodiment, the phase transfer catalyst is selected from thegroup consisting of tetraethyl ammonium chloride and the crown ether1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6 crown ether).

Formation Fluid

In the process, kerogen in subsurface shale is contacted with theoxidant. In one embodiment, the oxidant is a gaseous oxidant, and thecontacting involves the gas phase oxidant and the solid kerogen. In oneembodiment, the oxidant contacts the kerogen in the subsurface shale inliquid medium, otherwise termed a “formation fluid”. In this case, atleast a portion of the liquid medium may be the reactive fluid that isprepared in surface facilities and passed to the subsurface shalethrough an injection well. Likewise, at least a portion of the liquidmedium may be formation water that is naturally occurring in thesubsurface shale.

In one embodiment, reaction conditions and the composition of theformation fluid for converting kerogen into the mobile kerogen-basedproduct are selected to minimize the environmental effects of theprocess for extracting the kerogen-based product; and/or to maximize theconversion of kerogen into the mobile kerogen-based product; and/or tomaximize the selectivity of the reaction to C₁₀+ organic acids; and/orto minimize the conversion of the kerogen to CO₂.

The step of contacting the kerogen with the formation fluid in thesubsurface shale is generally conducted at or near an natural formationtemperature. In one embodiment, the contacting occurs at a temperaturein the range of between 0° C. and 200° C. In one embodiment, thecontacting occurs at a temperature of less than 200° C. above thenatural formation temperature. In one embodiment, the contacting occursat a temperature below a pyrolysis temperature of the kerogen. In onesuch embodiment, the contacting occurs at a temperature in one thefollowing ranges: between 10° C. and 150° C.; between 20° C. and 100°C.; or between 25° C. and 75° C. In one such embodiment, the formationfluid contacts the kerogen at a temperature of less than 150° C.; orless than 100° C.; or even less than 75° C. above the natural formationtemperature. In a non-limiting specific example, the contacting isconducted at a temperature of less than 50° C. above the naturalformation temperature. In one embodiment, the contacting is conductedunder conditions in which no added heat is supplied to the formationfluid and/or to the subsurface shale in contact with the formationfluid. In one embodiment, if heat is supplied during the kerogenconversion to meet the above-mention target temperature, it is suppliedsolely from exothermic chemical processes within the kerogen and/orwithin the subsurface shale in contact with the kerogen. As such, noexternal heating is provided. The contacting occurs at temperature belowpyrolysis temperature of the kerogen.

Generally, the kerogen in the subsurface shale is contacted with theformation fluid at or above natural formation pressure (i.e., thepressure of the subsurface shale formation in the region that includesthe kerogen), so as to maintain or increase the accessibility of thefluids to kerogen in the subsurface shale formation. In one suchembodiment, the formation fluid is provided to the formation at apressure above fracture pressure, so as to increase the accessibility ofthe formation fluid to the kerogen in the formation. Methods fordetermining the formation pressure and the formation fracture pressureare known. In one such embodiment, the formation fluid is provided tothe formation at a pressure of up to 1000 psig; or up to 750 psig; or upto 500 psig; or even up to 250 psig above the natural formationpressure. The natural formation pressure, as used herein, is thepressure of the subsurface shale formation, in the region of thekerogen, prior to human intervention with or in the formation. Methodsfor determining an natural formation pressure are known.

In one embodiment, the process includes contacting the kerogen in thesubsurface shale with an oxidant. The mobile kerogen-based productcomprises reaction products from the reaction of the oxidant with thekerogen. The step of creating a mobile kerogen-based product involves achemical modification of the kerogen. The chemical modification involvesat least some cracking of the kerogen, generating smallerkerogen-derived molecules that are correspondingly more mobile.

In one embodiment, a fluid, such as a formation fluid in contact withthe kerogen, facilitates the kerogen reactions. The formation fluid maybe caused to flow through the subsurface shale formation for an amountof time needed to reach a certain objective, e.g., a reduced oxidantconcentration target in the formation fluid, or a target amount ofmobile reaction products produced, or a target extent of conversion ofthe kerogen. The formation fluid may then be caused to flow through thesubsurface shale formation for an amount of time need to reach a certainobjective, e.g., a target removal of mobile reaction products, or atarget concentration of mobile reaction products in the formation fluid.In another embodiment, the process of providing reactive fluid to thekerogen may be a cyclic process, repeated until a target level ofkerogen conversion is achieved. In another embodiment, a formation fluidis suitable for both converting kerogen in the subsurface shale andabsorbing the reaction products to form the mobile kerogen-basedproduct, which is recovered for isolating the organic acids containedtherein.

In one embodiment, pumping is used to transport the mobile kerogen-basedproduct out of the subsurface shale formation, wherein such pumping canbe performed using techniques known to those of skill in the art.Conventional oil field practices (both flowing gas and pumping fluids,e.g., rod pumps, electrical submersible pumps, progressive cavity pumps,etc.) can be modified to provide reliability in a given producingenvironment. For example, modifications may require changes inmetallurgy, pressure limitations, elastomeric compositions, temperaturerating, and the like.

Production could use any standard producing process such as, but notlimited to, at least one well penetrating into the subsurface shaleformation as an injection well for providing fluids to the subsurfaceshale formation and at least one well penetrating into the subsurfaceshale formation as a production well for producing fluids from theformation, Huff-n-Puff (i.e., a single well is used as both the producerand injector), water flooding, steam flooding, polymer flooding, solventextraction flooding, thermal processes, diluent addition, steam assistedgravity drainage (SAGD), and the like.

Formation Fluid

The formation fluid is a fluid, such as an aqueous fluid, which is incontact with the kerogen in the subsurface shale formation. In oneembodiment, at least a portion of the formation fluid is supplied as areactive fluid from surface facilities. In one embodiment, the reactivesolution provided to the kerogen establishes a formation fluid incontact with the kerogen, or it supplements a formation fluid which isalready established, or which is naturally occurring in the subsurfaceshale formation in contact with the kerogen. In one embodiment, theformation fluid is derived from, or results from, formation water thatnaturally occurs within the formation. The formation fluid may bepresent and in contact with the kerogen in the formation, in smallquantities which merely wet the solid surfaces in the formation.Alternatively, the formation fluid may be present in sufficientquantities to flood the formation; or in any quantity between the wettedor flooded states.

The formation fluid is any fluid (including mixtures) that can, eitherby itself, with an agent combined with the fluid, or in combination witha solvent, chemically modify the kerogen so as to render it mobile andtherefore extractable. In one embodiment, the formation fluid comprisesan oxidant having a chemical property of oxidation. In one aspect, theoxidant is active for breaking chemical bonds in kerogen. In one aspect,the oxidant is active for breaking carbon-oxygen bonds in kerogen. Inone aspect, the oxidant is active for breaking carbon-carbon doublebonds in kerogen. In one aspect, the oxidant has a low activity forbreaking carbon-carbon single bonds in kerogen. In one aspect, theoxidant is active for producing mobile reaction products from kerogen.In one aspect, the oxidant is active for facilitating the mobilizationof hydrocarbons from kerogen in subsurface shale.

In one embodiment, at least a portion of the aqueous formation fluid isrecovered as a naturally occurring aqueous basic solution from one ormore subsurface aquifers; at least a portion of the naturally occurringaqueous basic solution may occur with the subsurface shale. Suitablenaturally occurring aqueous basic solutions have a pH of at least 7; orat least 8; or at least 8.5; or in the range of between 7 and 14. In onesuch embodiment, the naturally occurring aqueous basic solution floodsthe subsurface shale and is available for absorbing the convertedproducts, or is caused to flow from its source to the subsurface shalethat contains the converted products. In another such embodiment, thenaturally occurring aqueous basic solution is recovered from the aquiferthrough a well drilled into the aquifer. The recovered solution,optionally with added components, such as added carbonates,bicarbonates, oxides and/or hydroxides and/or added surfactants, ispassed through an injection well into the subsurface shale resource forextracting the hydrocarbon products present therein.

In one embodiment, at least a portion of the alkaline materials,including one or more of carbonates and bicarbonates and oxides andhydroxides, that are present in the formation fluid are derived fromnaturally occurring deposits. Naturally occurring sources of thealkaline materials are known. The following carbonate and bicarbonateminerals are non-limiting examples.

-   -   Sodium sesquicarbonate (Na₃H(CO₃)₂) is either a double salt of        sodium bicarbonate and sodium carbonate, or an equimolar mixture        of those two salts, with varying quantities of water of        hydration. The dihydrate, Na₃H(CO₃)₂.2H₂O, occurs in nature as        mineral trona.    -   Thermonatrite is a naturally occurring mineral form of sodium        carbonate Na₂CO₃.(H₂O).    -   Natron is a naturally occurring mixture of sodium carbonate        decahydrate (Na₂CO₃.10H₂O) and sodium bicarbonate (NaHCO₃),        often with relatively minor quantities of sodium chloride and        sodium sulfate.    -   Nahcolite is a naturally occurring form of sodium bicarbonate        (NaHCO₃).    -   Shortite is a naturally occurring form of a sodium-calcium        carbonate mineral (Na₂Ca₂(CO₃)₃).

As a non-limiting illustrative example, a reactive fluid is passed, viaan injection well, to a source of the alkaline materials within or nearthe subsurface shale resource to dissolve the alkaline materials intothe formation fluid before being passed to the formation fluid in thesubsurface shale formation. In some cases, liquid water is injectedunder sufficient pressure into the carbonate and/or bicarbonate sourceto cause the water to wet at least a portion of the source and todissolve at least some of the carbonate and/or bicarbonate into thewater.

In one such embodiment, the water that contains the dissolved alkalinematerials is caused to flow from the deposit in which it occurs to thesubsurface shale resource that contains the converted hydrocarbonproducts. In another such embodiment, the solution of the dissolvedalkaline materials is recovered from the aquifer through a well drilledinto the aquifer. The recovered solution, optionally with addedcomponents, such as added carbonates, bicarbonates, oxides and/orhydroxides, or added surfactants, is passed through an injection wellinto the subsurface shale resource for extracting the hydrocarbonproducts present therein.

In another such embodiment, at least a portion of the water isintroduced to the deposit of alkaline materials as steam, and in somecases as superheated steam, to facilitate the dissolution of thealkaline materials into the water. At least some of the steam condenses,dissolves the alkaline materials, and is passed to the subsurface shaleformation.

In one such embodiment, the process includes contacting the kerogen withthe fresh formation fluid, and producing a spent formation fluid whichcontains less than 20 wt. %, or less than 10 wt. %, or less than 5 wt. %of the oxidant, or less than 1 wt. % of the oxidant, or less than 0.5wt. % of the oxidant, or less than 0.1 wt. % of the oxidant. In oneembodiment, the reactivity of the formation fluid is enhanced byaddition of a combination of oxidants.

The formation fluid has a pH that is generally selected to balance thestability, reactivity and solubility of the oxidant in the formationfluid with the solubility and stability of the kerogen reaction productsin the formation fluid. Oxidants that exhibit high kerogen conversionactivity in aqueous fluid at pH values of at least 7 are generallysupplied to the subsurface shale formation in a basic solution (i.e.,basic formation fluid). In one such embodiment, the desired reactivesolution pH is achieved with the addition of an alkaline material to thereactive solution. Exemplary alkaline materials which are usefulinclude, for example at least one alkaline material selected fromcarbonates, bicarbonates, oxides, and hydroxides of, for example,sodium, potassium, calcium, and magnesium. An illustrative formationfluid contains a molar ratio of carbonate to bicarbonate in the rangefrom 5:95 to 95:5; or in the range from 10:90 to 90:10; or in the rangefrom 25:75 to 75:25.

The formation fluid may be further treated with acids or bases to tailorthe pH of the formation fluid, to, for example, account for thesolubility and/or stability of the oxidant or to increase the solubilityof the mobile organic acids produced during the kerogen conversionprocess. In one embodiment, the formation fluid that is supplied to thesubsurface shale has a pH of less than or equal to 7, or in the rangefrom 1.5 to 6.5. In another embodiment, the formation fluid that issupplied to the subsurface shale has a pH of at least 7. In this case,the pH of the formation fluid is selected both to facilitate thesolubility of organic acids in the formation fluid and to facilitate thechemical stability and reactivity of the oxidant at subsurface shaleformation conditions. In one embodiment, the formation fluid is suppliedto the subsurface shale formation at a pH in the range of 7 to 14; or inthe range of 7 to 9.

Oxidants that exhibit high kerogen conversion activity in aqueous fluidat pH values of less 7 are generally supplied to the subsurface shaleformation in acidic solution (i.e., acidic formation fluid). In one suchembodiment, the desired reactive solution pH is achieved with theaddition of an acidic material to the reactive solution. Mineral acids,such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acidor organic acids such as one or more of the carboxylic acids having from2 to 15 carbon atoms, or mixture thereof may be used. With thecarboxylic acids, monoacids, diacids, or triacids may be used. In oneembodiment, CO₂ is supplied to the formation fluid, either duringpreparation, while the fluid is being passed to the kerogen or incontact with the kerogen. When CO₂ is supplied to the formation fluid inthe formation, it may be supplied as a subcritical gas, a dense phasegas or a supercritical fluid. In other embodiments, it may be suppliedin combination with a liquid fluid. The pH of the prepared formationfluid will generally be selected on the basis of the specific oxidantthat is being used. In one embodiment, the pH of an acidic formationfluid will be less than 7, including a pH in the range from 1.5 to 6.5.

The formation fluid may further contain other components for, e.g.,enhancing the reactivity of the reactive components, for enhancing theaccessibility of the formation fluid to the kerogen, or for enhancingthe dissolution, absorption, or dispersion of mobile reaction productsinto the formation fluid.

Formation Water

Formation water, a naturally occurring liquid source within at leastsome kerogen deposits in subsurface shale, is a suitable source for atleast a portion of the formation fluid used for converting kerogen andrecovering useful products. Some kerogen deposits are directly incontact with formation water. Other kerogen deposits are wetted byresidual formation water. In other deposits, the formation water aquiferis remote from the kerogen deposit which is being exploited forrecovering useful products. When sufficient formation water is present,either in contact with the kerogen or sufficiently near the kerogendeposit to be passed to the kerogen deposit, the formation water may beuseful as a source of at least some of the components of the formationfluid.

Certain subsurface shale formations, such as the Green River Shale, arecharacterized by limestone deposits that produce formation wateraquifers having a basic pH (i.e., pH greater than 7). In one embodiment,formation waters are useful as a source or a component of the formationfluid. In an exemplary process, oxidant is provided to formation waterto form the formation fluid, which facilitates the conversion of kerogenat a temperature in the range of between 0° C. and 200° C. to formorganic acids.

In the case in which the kerogen is naturally in contact with formationwater that is suitable for the process, the process includes providingan oxidant to the formation water to produce the formation fluid. Forformations in which the formation water having the desired properties isin an aquifer separate from (or remote to) the kerogen, the formationwater may be caused to pass from the remote aquifer to the kerogen. Thismay be achieved, for example, by causing the formation water to passfrom the remote aquifer through a borehole which is drilled into theformation water aquifer. In one embodiment, the formation water ispassed through the borehole to surface facilities, and processed byaddition of oxidant and then provided to the kerogen. In anotherembodiment, the formation water is passed through the borehole directlyto the kerogen in the subsurface shale formation.

When at least a portion of the mobile kerogen-based product is withdrawnfrom the formation, additional formation fluid in the region of thekerogen is produced by flowing additional formation water to, andcontacting, the kerogen in the subsurface shale formation to replace thefluid that was withdrawn. In one embodiment, one or more oxidants areprovided to the additional formation water that flows into contact withthe kerogen.

As stated, suitable formation water has a pH of at least 7, or in therange from 7 to 14, or in the range from 12 to 14. In one embodiment,the formation water comprises an alkaline material selected from thegroup consisting of a carbonate, a bicarbonate, an oxide, and ahydroxide. An exemplary alkaline material is selected from the groupconsisting of sodium carbonate, sodium bicarbonate, and sodiumhydroxide, or mixtures thereof.

In the process, a formation fluid which comprises formation water and anoxidant contacts the kerogen for a time sufficient to reduce the oxidantconcentration to a target low level. In one embodiment, the formationfluid is caused to contact with kerogen for a time sufficient to reducethe oxidant concentration in the formation fluid to less than 0.5 wt. %,or for a time sufficient to reduce the oxidant concentration in theformation fluid to less than 0.1 wt. %.

Use of formation water as a component of the formation fluid permits theuse of a cyclic process to convert kerogen and recover useful products.An exemplary cyclic process comprises the steps of: (a) providing anoxidant to formation water that is in contact with kerogen in subsurfaceshale to form a formation fluid; (b) contacting the kerogen in thesubsurface shale with the formation fluid at a temperature in the rangeof between 0° C. and 200° C. to form organic acids; (c) recovering atleast a portion of the organic acids from the subsurface shale formationto form a mobile kerogen-based product; (d) withdrawing at least aportion of the mobile kerogen-based product from the formation; (e)providing additional oxidant to the formation water in contact with thekerogen; and (f) repeating steps (b), (c), (d), and (e) a multiplicityof cycles, and converting at least 50 wt. % of the kerogen to organicacids. In one embodiment, the cyclic process also includes recyclesteps, including: isolating at least a portion of the organic acids fromthe mobile kerogen-based product; recovering an organic acid leanaqueous fluid; and providing at least a portion of the organic acid leanaqueous fluid, in combination with added oxidant, to the formation fluidin contact with the kerogen.

Organic Acids

In the process, the oxidant contacts the kerogen to form organic acids.The organic acids may be saturated, unsaturated, or polyunsaturated. Inone embodiment, at least a portion of the organic acids are branched;the branching functional groups may be paraffinic, olefinic or cyclic.Cyclic branching functional groups may be saturated, unsaturated oraromatic. The organic acids may also contain nitrogen and/or sulfuratoms. In one embodiment, the organic acids are monoacids (a singlecarboxyl functional group in non-ionized or ionized form per molecularunit), or diacids (two carboxyl functional groups per molecular unit),or triacids (three carboxyl functional groups per molecular unit), orhigher. Mobile kerogen fragments, including kerogen fragments having amolecular mass of up to 12,000 to 15,000 Daltons or higher, may havemultiple carboxyl functional groups that serve to render these fragmentsmobile in an aqueous medium. These high molecular weight fragments aregenerally mobilized in the fluid as a slurry, rather than as a puresolution. Under some conditions, the organic acids are present as salts.An exemplary sodium salt of an organic acid contains the carboxylfunction group represented by —COO—Na+.

The molecular weight of the organic acids covers a very wide range,including from low molecular weight acids, such as the monoacid, aceticacid, and the diacid, oxalic acid, to high molecular weight kerogenfragments, having a molecular mass of up to 15,000 daltons or higher,and comprising at least one carboxylic acid functional group. In oneembodiment, these kerogen fragments have a lower molecular mass than thenaturally occurring kerogen itself, but with the general characteristicchemical and conformational complexity of the kerogen structures fromwhich they are derived. Such high molecular weight acids are soluble in,or otherwise mobile in, high pH solutions, such as solutions having a pHof at least 7; or at least 8; or at least 8; or in the range of between12 and 14. Accordingly, in one embodiment, at least 10 wt. %, or atleast 30 wt. %, or at least 50 wt. % of the organic acids in the mobilekerogen-based product is in the C₃₅+ range. In one embodiment, at least20 wt. % of the C₃₅+ organic acids has a molecular mass number ofgreater than 1000 daltons.

In one embodiment, a significant fraction of the organic acids are alsoin the C₆ to C₂₀ carbon number range. In one such embodiment, at least10 wt. % of the organic acids in the mobile kerogen-based product are inthe C₆ to C₂₀ range, or in the C₆ to C₁₆ range, or in the C₈ to C₁₄range or in the C₈ to C₁₂ range. In one such embodiment, at least 20 wt.% of the C₃₅− organic acids is in the C₈ to C₁₂ range. Maintainingreaction conditions to minimize the amount of oxidation of the kerogenwhile ensuring that the reaction products are mobile has the benefit ofdecreased oxidant consumption, minimum formation of carbon dioxideproduct, and reduced hydrogen consumption during the hydrogenation ofthe acid products during an upgrading step.

In general, the mobile kerogen-based product contains at least one ofthe following organic acids and hydrocarbons: monoacids, diacids,branched monoacids, branched diacids, isoprenoid acids, iopanoic acids,gamma keto acids, keto monoacids, keto diacids, and n-alkanes. In therange from 10 wt. % to 90 wt. % of the C₃₅− organic acids in the mobilekerogen-based product are monoacids. In one such embodiment, in therange from 10 wt. % to 50 wt. % of the C₃₅− organic acids are monoacids.Likewise, in the range from 10 wt. % to 90 wt. % of the C₃₅− organicacids in the mobile kerogen-based product are diacids. In oneembodiment, at least 30 wt. % of the C₃₅− organic acids are diacids. Inone such embodiment, in the range from 30 wt. to 90 wt. % of the C₃₅−organic acids are diacids. In one embodiment, in the range from 1 wt. %to 30 wt. %, or in the range from 1 wt. % to 20 wt. %, or in the rangefrom 1 wt. % to 10 wt. % of the C₃₅− organic acids in the mobilekerogen-based product are gamma keto acids.

Mobile Kerogen-Based Product

In one embodiment, the organic acids are mobilized to produce a mobilekerogen-based product. The mobile kerogen-based product generallycontains at least 1 wt. % organic acid derived products; or at least 2wt. % organic acid derived products; or at least 5 wt. % organic acidderived products. In some situations, the organic acid derived productsare present in the product at a concentration in the range from 5 wt. %to 50 wt. %; or at a concentration in the range from 10 wt. % to 40 wt.%. The ratio of organic acid derived products to other hydrocarbons inthe mobile kerogen-based product will depend on the source of thehydrocarbons, but is expected to range from 10% organic acid derivedproducts to 100 wt. % organic acid derived products.

It is believed that organic acids comprise a significant portion of thekerogen based product formed from reaction of oxidants on the kerogen.However, when the organic acids are mobilized, organic acid reactionproducts may be involved. As such, mobilization of the organic acids mayinvolve, for example, neutralization, dimerization and esterification ofthe organic acids.

Thus, in one embodiment, the mobile kerogen-based product may compriseorganic acid as organic acids. In one embodiment, the mobile kerogenbased product may comprise organic acids as organic acid anionicmoieties (RCOO—) or organic acid salts (RCOO— M+). The cation (M+) ofthe organic acid salts can be cations that are naturally present in theformation, for example, sodium, potassium, calcium and magnesium. In oneembodiment, the mobile kerogen based product may comprise organic acidsas esters. Exemplary esters include methyl and ethyl esters. In oneembodiment, the mobile kerogen-based product may comprise organic acidsin a form selected from the group consisting of organic acids, organicacid salts, anionic organic acid moieties, organic acid esters, andmixtures thereof.

The mobile kerogen-based product may further include components tofacilitate extraction of reaction products from the kerogen. Thesecomponents may include, for example, one or more of a solvent or solventmixture; alkaline materials; surfactants; organic and/or inorganicacids; organic and/or inorganic bases; soluble organic compounds such asalcohols, ethers, esters, ketones, aldehydes, and the like. In oneembodiment, the mobile kerogen-based product is an aqueous phase fluidcontaining the organic acid derived products, which are dissolved,dispersed, or suspended in the aqueous phase fluid.

As used herein, the term “mobile kerogen-based product” refers to thefluid containing the mobile reaction products that is withdrawn from theformation. The mobile kerogen-based product is formulated to keep themobile reaction products in a mobile phase by, for example, maintainingthe pH of the mobile kerogen-based product at or above a target minimumlevel. In one embodiment, the mobile kerogen-based product contains atleast one surfactant to further stabilize the reaction products as theyare withdrawn from the formation. The mobile kerogen-based product maycontain residual oxidants; however, withdrawing the mobile reactionproducts after reacting and/or removing most or all of the activeoxidant serves to minimize the secondary oxidation reactions of themobile reaction products.

In one embodiment, the mobile kerogen-based product further compriseshydrocarbons other than organic acids, including those commonly termed“bitumen”, that are present in the subsurface shale and may be mobilizedin the mobile kerogen-based product. This hydrocarbon fraction consistsof both aliphatic and aromatic components. The aliphatic component canfurther be divided into acyclic alkanes, referred to as paraffins, andcycloalkanes, referred to as naphthenes. The lightest hydrocarbons, suchas methane and ethane, are gases at room temperature and pressure;heavier hydrocarbons are liquids whose viscosity increases with thenumber of carbons. At least a portion of these hydrocarbons are solublein carbon disulfide.

In general, little or no active oxidant remains in the mobilekerogen-based product. The oxidant concentration in the mobilekerogen-based product is sufficiently low to minimize or to preventadditional oxidation reactions of the mobile reaction products in thefluid. In an embodiment, the mobile kerogen-based product contains lessthan 0.5 wt. % of an oxidant. In an embodiment, the mobile kerogen-basedproduct contains less than 0.1 wt. % oxidant. In an embodiment, themobile kerogen-based product contains an amount of oxidant that is belowthe detection limit for that oxidant.

In one embodiment, the mobile kerogen-based product further includes acarrier fluid, which may be an aqueous carrier fluid, an organic carrierfluid, or a combination of the two. In one embodiment, the carrier fluidincludes one or more components of a recycle fluid from the process. Inone embodiment, the carrier fluid contains naturally occurring formationwater which has a pH in the suitable range. In a further embodiment, theformation water contains alkaline materials which have been dissolvedinto the formation water from alkaline sources, such as nahcolite,within the formation.

In one embodiment, the organic acid reaction products are mobilized at apH of at least 7, or at a pH in a range from 7 to 14. The pH of themobile kerogen-based product into which organic acids are extracted,following conversion of the kerogen, may, under some conditions, have apH in a range from 7 to 14 by reason of contact with alkaline materialsin the subsurface shale. Alternatively, at least a portion of thealkaline materials present in mobile product may be provided fromsurface facilities. Exemplary alkaline materials which are usefulinclude, for example at least one alkaline material selected fromcarbonates, bicarbonates, oxides and hydroxides of, for example, sodium,potassium, calcium, and magnesium. In an illustrative process, organicacids are extracted from kerogen in contact with alkaline materials,such that a molar ratio of carbonate to bicarbonate in the range from5:95 to 95:5; or in the range from 10:90 to 90:10; or in the range from25:75 to 75:25.

The pH of the mobile fluid in contact with the kerogen, for extractingorganic acid reaction products, is tailored for the particular organicacids to be extracted into and absorbed by the mobile product. Lowmolecular weight acids are soluble in fluids having a pH at or near theneutral range (i.e. a pH in a range from 6 to 8). High molecular weightkerogen fragments may be mobilized as a colloid or slurry in the mobileproduct at a pH in a range from 12 to 14.

Formation of the mobile kerogen-based product may be facilitated by thepresence of one or more organic solvents. Suitable organic solvents areselected to remain in a liquid phase, and to maintain the reactionproducts in solution, at temperature and pressure conditions within thesubsurface shale. In one embodiment, a suitable organic extraction fluidis one in which at least a portion of the organic acids are soluble.Exemplary organic extraction fluids contain aromatic compounds such asbenzene, toluene and xylene; nitrogen containing solvents such as NMP,amines, and amides; oxygenates containing compounds such as acids,ketones, esters and aldehydes; paraffins and naphthenes; olefins and thelike. Illustrative organic solvents include refinery streams boiling inthe range from 100° C. to 500° C., such as diesel fuel or naphtha.

In one embodiment, the mobile kerogen-based product may include carbondisulfide. Hydrogen sulfide, in addition to other sulfur compoundsproduced from the formation, may be converted to carbon disulfide usingknown methods. Suitable methods may include oxidation reaction of thesulfur compound to sulfur and/or sulfur dioxides, and by reaction ofsulfur and/or sulfur dioxides with carbon and/or a carbon containingcompound to form the carbon disulfide formulation.

Product Recovery

The step of extracting and absorbing the organic acid reaction productsinto the mobile kerogen-based product fluid is generally conducted at ornear the natural formation temperature. In one such embodiment, theabsorbing is conducted at a temperature of less than 200° C.; or lessthen 150° C.; or less than 100° C.; or even less than 75° C. above thenatural formation temperature. In one such embodiment, the absorbing isconducted at a temperature in the range of between 0° C. and 200° C.; orin the range of between 10° C. and 150° C.; or in the range of between20° C. and 100° C.; or even in the range of between 25° C. and 75° C. Ina non-limiting specific example, the absorbing is conducted at atemperature of no greater than 50° C. above the natural formationtemperature.

In one embodiment, the absorbing is conducted under conditions in whichno added heat is supplied to the formation fluid and/or to thesubsurface shale in contact with the formation fluid. In one embodiment,if heat is supplied during the kerogen conversion to meet theabove-mention target temperature, it is supplied solely from exothermicchemical processes within the kerogen and/or within the subsurface shalein contact with the kerogen. In one embodiment, the absorbing isconducted at a temperature below pyrolysis temperature.

Generally, the organic acids in the subsurface shale are absorbed intothe mobile kerogen-based product at or above formation pressure (i.e.,the pressure of the subsurface shale formation in the region thatincludes the kerogen), so as to maintain or increase the accessibilityof the fluids to kerogen in the subsurface shale formation. In oneembodiment, the organic acid reaction products are extracted from thekerogen and into the mobile kerogen-based product at a pressure of up to1000 psig above the formation pressure; or up to 750 psig above theformation pressure; or up to 500 psig above the formation pressure; oreven up to 250 psig above the formation pressure. Injection of a gasinto the formation may result in a viscosity reduction of some of thehydrocarbon products in the formation.

In one embodiment, a formation fluid is maintained in contact with thekerogen until a target amount of mobile reaction products have beenabsorbed by the formation fluid, i.e., for a time sufficient to producea mobile kerogen-based product which contains at least 1 wt. % organicacids; or at least 2 wt. % organic acids; or at least 5 wt. % organicacids. Progress toward reaching the target amount may be monitored, forexample, by withdrawing the fluids to the surface for analysis, byanalyzing the fluids in the subsurface shale formation, or by analyzingthe fluids in a well extending into the formation.

In one embodiment, a formation fluid that is suitable for mobilizing thereaction products has a pH of greater than a target value, e.g., greaterthan 7, and the formation fluid is maintained in contact with thekerogen for a time during which the pH of the formation fluid remainshigher than the target minimum pH value. When the pH approaches or dropsbelow the target minimum, the formation fluid may be removed from thesubsurface shale, its alkaline content may be supplemented with alkalineadditives, or it may be supplemented with added reactive fluid.

In an exemplary process illustrated in FIG. 1, a reactive fluid isprepared in a preparation step 10 by mixing an oxidant 2 with a carrierfluid 4, which may be aqueous or organic. Mixing devices for mixing theoxidant with the carrier fluid to make the reactive fluid are wellknown. In one embodiment, the oxidant that is used is effective forreacting with kerogen in an alkaline medium; under these conditions thefluid may optionally be mixed with an alkaline material 6 to result in afluid having a pH of at least 7.

The reactive fluid mixture 15 is passed to the kerogen in the subsurfaceshale formation in step 20 via a first (e.g., injection) well that hasbeen drilled to penetrate the subsurface formation to provide access tothe kerogen within the formation. The reactive fluid combines with afluid already present to form a formation fluid 25, in contact with thekerogen. In one embodiment, the subsurface shale formation has beenfractured to enhance the permeability of the shale to the oxidant and toincrease the accessibility of the kerogen component to this fluid. Instep 30 the oxidant reacts with the kerogen to produce a mobilekerogen-based product 35, which is produced to the surface in step 40.In one embodiment, multiple reactive fluid batches are provided to theformation fluid, prior to recovery of the mobile kerogen-based product.The timing of each reactive fluid addition depends, at least in part, onthe progress of the kerogen conversion, and on the relative reactivityof the formation fluid in contact with the kerogen. For example, anotherreactive fluid batch may be provided to the formation fluid when theoxidant concentration in the formation fluid falls below 30 wt. %, orbelow 20 wt., or below 10 wt. % of the initial oxidant concentration inthe fluid.

The mobile kerogen-based product 45 produced at the surface is treatedin step 50 for isolation and recovery of the organic acids and othermobile hydrocarbons 75. In one embodiment, at least a portion of thereaction products recovered from the kerogen conversion is absorbed bynaturally occurring alkaline enriched water that is present in thesubsurface shale. In the illustrative process shown in FIG. 1, theorganic acids 75 isolated in step 50 are subjected to further processingin step 70. In an embodiment of the illustrative process, an organicacid lean fluid 55 that is produced from the isolation step 50 isfurther treated in step 80 for recycle 85 to the subsurface shaleformation.

In an exemplary process illustrated in FIG. 2, and with furtherreference to the descriptions above relating to FIG. 1, a mobilekerogen-based product 35 is produced to the surface in step 40. Themobile kerogen-based product 45 produced at the surface is combined withan organic extraction fluid 115 and the combination treated in step 50for isolation and recovery of the organic acids and other mobilehydrocarbons 75. The organic acids 75 isolated in step 50 are subjectedto further processing in step 70. In an embodiment of the illustrativeprocess, an organic acid lean fluid 55 that is produced from theisolation step 50 is further treated in step 80 for recycle 85 to thesubsurface shale formation. An acid lean extractant 105 from step 50 isrecycled and combined with organic extraction fluid 115.

In an exemplary process illustrated in FIG. 3, a reactive fluid 115 isprepared in a preparation step 110 by mixing an oxidant 102 with acarrier fluid 104, which may be aqueous or organic. Mixing devices formixing the oxidant with the carrier fluid to make the reactive fluid arewell known. In one embodiment, the oxidant that is used is effective forreacting with kerogen in an alkaline medium; under these conditions thefluid may optionally be mixed with an alkaline material 106 to result ina fluid having a pH of at least 7.

The reactive fluid mixture 115 is passed to the kerogen in thesubsurface shale formation in step 120 via a first (e.g., injection)well that has been drilled to penetrate the subsurface formation toprovide access to the kerogen within the formation. The reactive fluidcombines with a fluid already present to form a formation fluid 125, incontact with the kerogen. In one embodiment, the subsurface shaleformation has been fractured to enhance the permeability of the shale tothe formation fluid and to increase the accessibility of the kerogencomponent to this fluid. In step 130, the oxidant reacts with thekerogen to form organic acids 135.

A extractive fluid 145 is prepared in preparation step 140 by mixing analkaline material 142 with an aqueous carrier fluid 144 and optionallywith a surfactant 146. The extractive fluid 145 is combined into theformation fluid in step 150 for mobilizing the organic acids and to formthe mobile kerogen-based product 155, which is recovered. The mobilekerogen-based product 155 is treated in 160 to isolate organic acids175, which may be further processed in 170.

Isolating the organic acids further produces an organic acid lean fluid165, containing a reduced amount of organic acids. This fluid isprepared for return to the formation as a recycle fluid 185. Prior torecycling, the organic acid lean fluid may be conditioned in step 180for recycling to the formation. Typical conditioning steps include, forexample, removing inorganic salts, removing at least a portion of theremaining organic acids, including C₁ to C₁₀ organic acids, and removingother organic material from the fluid.

During some applications of the process, it may be desirable to contactkerogen in the subsurface shale with multiple oxidant treatments. Witheach treatment, an oxidant or a reactive fluid containing the oxidant isprovided to the kerogen, for contacting the kerogen for a timesufficient to reduce the amount of oxidant to a target low level.Reaction products, including organic acids from the oxidation ofkerogen, are mobilized by extracting, dissolving, absorbing or otherwisedispersing these products into an alkaline containing mobilekerogen-based product having a pH of at least 7. In one embodiment, theremoval of reaction products following the first oxidation treatment isfacilitated by the presence of alkaline materials in the formationfluid, provided, for example, by supplying the alkaline materials to theformation fluid, by providing alkaline formation water to the formationfluid, or by adding a reactive fluid containing the alkaline material tothe formation fluid.

Following removal of the mobilized reaction products in the mobilekerogen-based product, a second treatment of oxidant is supplied to theformation fluid in contact with the kerogen. As with the firsttreatment, the oxidant may be supplied in pure form, or dissolved orotherwise associated with a carrier fluid, such as an aqueous carrierfluid, in a reactive fluid. The oxidant used in the first and secondtreatments may be the same or different. In one embodiment, the oxidantsused in the first and second treatments are the same. Likewise, theconcentration of the oxidant in the first treatment and the secondtreatment may be the same or different. Following the second treatment,additional mobilized reaction products are removed from the subsurfaceshale formation in a mobile kerogen-based product. In one embodiment,the removal of reaction products following the second oxidationtreatment is facilitated by the presence of alkaline materials in theformation fluid, provided, for example, by supplying the alkalinematerials to the formation fluid, by providing alkaline formation waterto the formation fluid, or by adding a reactive fluid containing thealkaline material to the formation fluid. In another embodiment, thekerogen is contacted with multiple oxidant treatments, which is followedby removal of a mobile kerogen-based product containing at least aportion of the organic acids formed in the multiple treatments.

Generally sufficient oxidant is supplied to the formation fluid toresult in a formation fluid containing in the range of 0.1 wt. % to 40wt. % oxidant. In one embodiment, sufficient oxidant is supplied toresult a fluid containing in the range of 0.1 wt. % to 25 wt. %; or inthe range of 1 wt. % to 15 wt. % of the oxidant. Generally, at least 50wt. % of the oxidant is consumed during each treatment. In someembodiments, at least 60 wt. %, or at least 70 wt. %, or at least 80 wt.% of the oxidant is consumed during each treatment. Generally, at least30 wt. % of the kerogen is converted during the multiple treatmentprocess. In one embodiment, at least 50 wt. %, or at least 60 wt. %, orat least 70 wt. % of the kerogen is converted during the multipletreatment process.

In one embodiment, the process for extracting a kerogen-based productincludes causing the mobile kerogen-based product to flow through thesubsurface shale formation and to a second (e.g., production) well thathas been drilled to penetrate the subsurface formation to withdrawfluids from the formation. The formation fluid in contact with thekerogen causes some of the kerogen to react and form mobile reactionproducts, which are recovered from the subsurface shale to surfacefacilities for isolation and recovery of the mobile reaction products.In one embodiment, at least a portion of the mobile reaction productsare absorbed by the formation fluid and the resulting mobilekerogen-based product is recovered from the subsurface shale formation.

In one embodiment, the reactive fluid is caused to flow into thesubsurface shale formation from the injection well until a targetpressure higher than formation pressure is reached within the formation.The flow of the reactive fluid is then slowed or stopped and theresultant formation fluid mixture is maintained in contact with thekerogen, while converting kerogen in the subsurface shale to a mobilekerogen-based product and producing an oxidant-depleted formation fluid.At least a portion of the formation fluid mixture may be removed fromthe kerogen when, for example, the reactivity of the formation fluid isdepleted below a target amount, or the pH of the formation fluid haschanged beyond a target pH range, or the amount of reaction productsfrom kerogen conversion which has been absorbed by the formation fluidhas met or exceeded a target amount. Alternatively, additional oxidantmay be provided to the formation fluid, or the oxidant may beregenerated in situ. In one embodiment, the mobile kerogen-based productis at least partially removed from the subsurface shale by reducing thepressure on the shale and permitting the formation fluid to flow into awell for removal to the surface. In one embodiment, the mobilekerogen-based product is at least partially removed by displacement withadditional reactive fluid added to the formation through an injectionwell.

In one embodiment, oxidant is maintained in contact with the kerogenuntil a target amount of mobile reaction products are produced and/orare absorbed into the formation fluid. Progress toward reaching thetarget amount may be monitored, for example, by withdrawing the fluidsto the surface for analysis, by analyzing the fluids in the subsurfaceshale formation, or by analyzing the fluids in a well extending into theformation. In one embodiment, the formation fluid is maintained incontact with the kerogen up to a target kerogen conversion. In one suchembodiment, the formation fluid is maintained in contact with thekerogen until at least 10 wt. %; or at least 30 wt. %; or at least 50wt. %; or at least 60 wt. %; or at least 70 wt. %; or even at least 80wt. % of the kerogen is converted to mobile reaction products. In oneembodiment, the formation fluid is maintained in contact with thekerogen for a time sufficient to reduce the concentration of the oxidantto a target value. Reducing oxidant concentration to low levels duringreaction facilitates the formation of high amounts of large mobilekerogen fragments and the formation of low amounts of CO₂ duringreaction of the kerogen. For example, less than 15 wt. %; or less than10 wt. %; or less than 5 wt. % of the kerogen is converted to CO₂ duringreaction with the formation fluid. In one embodiment, the formationfluid is maintained in contact with the kerogen for a period of greaterthan 1 hour; or in another embodiment for a period of greater than 4hours, or for a period of greater than 12 hours. In another embodiment,the formation fluid is maintained in contact with the kerogen for aperiod in the range from 1 hour to 45 days; in another embodiment from12 hours to 20 days; in another embodiment from 1 day to 7 days, inorder to reduce the concentration of the oxidant to a target value inthe spent formation fluid.

The process may further include monitoring the extent of reaction of thekerogen. For example, a fluid sample, such as the formation fluid, maybe removed from the subsurface shale formation and analyzed for theoxidant component. Alternatively, the progress of the reaction may bemonitored using a downhole analyzer to determine the concentration ofthe oxidant component in the formation fluid. An analyzer suited todetermining a quantity of the oxidant may be inserted into, orintimately contacted with the fluids in the subsurface shale formation.

In other embodiments, the process further comprises monitoring thekerogen conversion using the amount of mobile reaction products in thesubsurface shale formation. As with the oxidant reactive componentdescribed above, the amount of mobile reaction products may bedetermined from an analysis of fluids recovered from the formation, orfrom a downhole analysis tool suited for analyzing the amount ofreaction products.

In an embodiment, additives are supplied to the formation fluid in thesubsurface shale formation to further the reactivity of the formationfluid mixture and/or to facilitate the formation of the mobilekerogen-based product. In one such embodiment, additional oxidants maybe supplied from surface facilities through the one or more injectionwells provided for supplying fluids to the kerogen. The oxidant additivemay be the same as the oxidant in the formation fluid, or different. Ingeneral, the selection of the oxidant additive and the target increasein reactivity of the formation fluid after treatment with the oxidantadditive depends on a number of factors relating to the formation andthe kerogen within the formation. For example, an oxidant additive maybe supplied to the formation fluid to maintain a low reactivity of theformation fluid, to facilitate the formation of large kerogen fragmentsin the mobile kerogen-based product, rather than light acids or CO₂. Ina non-limiting example, an oxidant concentration in the range from 1 wt.% to 15 wt. % is maintained through the reaction phase, with additionaloxidant being supplied to the formation fluid to maintain aconcentration within this range.

In one embodiment, CO₂ is supplied as an additive to the shale formationduring the reaction step to control the pH of the formation fluidmixture. The additive CO₂ may be injected into the shale formation as apressurized gas or as a supercritical fluid, depending, at least inpart, on the formation pressure in the vicinity of the kerogen.

In one embodiment, depending on the conditions and formation fluidsemployed and on the kerogen bonds that are broken, it is possible togenerate a mobile kerogen-based product that is tailored so as tominimize recovery of heavy metals and/or other undesirable materials, orto increase recovery by reducing char and/or other carbon residues.Accordingly, it is possible to generate a mobile kerogen-based productthat requires little or no additional refining.

Trona Water

In one embodiment, organic acids occur in naturally occurring aqueousfluids. Most of these naturally occurring aqueous fluids aresubterranean; they can be recovered by penetrating the aquifer with awell and pumping the aqueous fluid to the surface for isolation andupgrading of the organic acids contained therein. While the source ofthe organic acids in the naturally occurring aqueous fluids has not beenspecifically identified, it is believed that at least a portion of theorganic acids are derived from the conversion of subterranean kerogenover geological timeframes. These naturally occurring aqueous solutionsthat contain significant organic acids contents are known by a number ofdifferent names. The term “Trona water” is frequently applied at leastone source.

The naturally occurring aqueous fluid is water based, with substantialquantities of organic acids, which are stabilized in the fluid by highfluid pH. In one embodiment, the naturally occurring aqueous fluid isrecovered from an underground reservoir or aquifer, or from a lake,river or body of water which is supplied from an underground reservoiror aquifer. In general, the naturally occurring aqueous fluid isrecovered from a natural source as a liquid phase solution, or as aslurry, suspension or emulsion.

In producing a naturally occurring aqueous solution, in one embodiment,the producing step includes recovering an aqueous fluid from a body ofwater, such as stream, a river, a lake, or a pond. In one suchembodiment, the water in the body of water originates from asubterranean reservoir. In a further embodiment, the producing stepincludes recovering the naturally occurring aqueous fluid directly froma subterranean reservoir through a well penetrating the earth to thesubterranean reservoir. Methods for producing the well, preparing thewell for recovery of liquids and recovering liquids such as aqueousfluids from a subterranean reservoir are well known. In one embodiment,the produced aqueous fluid, either from a surface body of water or froma subterranean reservoir, is treated as described herein to isolate theorganic acids contained therein.

These organic acids may be present in the aqueous fluid at aconcentration of greater than 1 wt %. In some situations, the organicacids are present at a concentration of greater than 2 wt. % or even 5wt. %. In some situations, the organic acids are present at aconcentration in the range of from 1 wt. % to 50 wt. %, or from 1 wt. %to 40 wt. %, or from 1 wt. % to 30 wt. %. The ratio of organic acids toother hydrocarbons in the aqueous fluid will depend on the source of thehydrocarbons, but is expected to range from 10% organic acids toapproaching 100 wt. % organic acids, with at most measurably traceamounts of other functional types.

In one embodiment, the aqueous fluid contains one or a mixture ofinorganic components. In one such embodiment, at least one of theinorganic components contributes to increasing the solubility of thehydrocarbon component in the aqueous solution. For example, thesolubility of organic acids in the aqueous solution may be enhanced byinorganic components that are alkaline in aqueous solution. Inembodiments, the aqueous fluid has a pH of at least 7, or at least 8, orat least 8.5, or in the range of between 7 and 14. In one embodiment,the aqueous fluid pH is achieved with the presence of an alkalinematerial to the aqueous solution. Exemplary alkaline materials include,for example at least one alkaline material selected from carbonates,bicarbonates, oxides, and hydroxides of, for example, sodium, potassium,calcium, and magnesium. In one embodiment, the aqueous fluid comprisesan alkaline material selected from the group consisting of sodiumcarbonate, sodium bicarbonate, and sodium hydroxide. At least a portionof the alkaline material may be in the form of carbonate and/orbicarbonate minerals. In an illustrative process, organic acids areextracted from kerogen in contact with alkaline materials, such that amolar ratio of carbonate to bicarbonate in the range from 5:95 to 95:5;or in the range from 10:90 to 90:10; or in the range from 25:75 to75:25.

The organic acids are isolated from the mobile kerogen-based product insurface facilities. In one embodiment, isolating the organic acidsinvolves one or more of pH titration, fractional neutralization,esterification, extraction, distillation, membrane separation, frothflotation, phase separation, electrostatic separation, filtering,centrifugal separation, coalescence, precipitation, thermal separation,steam distillation, or any combination thereof, in any order.

Reducing the pH of the mobile kerogen-based product generally involvesadding an acid to the product. Suitable acids for this step include themineral acids, such as sulfuric acid, hydrochloric acid, nitric acid,phosphoric acid or mixtures thereof. In one embodiment, addition of CO₂to the mobile kerogen-based product lowers the pH sufficiently toproduce a second phase of the high molecular weight organic acids, whichmay be liquid or solid. In one embodiment, sufficient acid is added tothe mobile kerogen-based product to reduce the pH of the product to a pHin a range from 7 to 12; in another embodiment to less than 7; inanother embodiment in a range from 1.5 to 7; and in another embodimentin a range from 1.5 to 6.5. In one embodiment, the pH is lowered to a pHin the range from 9 to 12 to isolate C₃₅+ organic acids, some of whichat least are solid C₃₅+ organic acids. In another embodiment, the pH islowered in a single step to a pH in a range from 1.5 to 6.5, to producean organic acid syncrude comprising organic acids in the C₁₂+ range. Inother embodiments, the pH is lowered in multiple steps, with organicacid products being isolated and recovered after each step.

In one embodiment, after each change in pH, at least a portion of theorganic acids that form a separate liquid or solid phase from the mobilekerogen-based product is isolated. In one embodiment, the mobilekerogen-based product is contacted with an organic extraction fluideither before, during or after the pH change, for extracting at least aportion of the acids from the mobile kerogen-based product into theorganic extraction fluid.

The amount of acid that is added is controlled by a number of factorsthat are specific to the particular process, including the target pH ofthe acidified product, the chemical character of the dissolved organicacids and the composition of the product prior to an acidification step.For example, a mobile kerogen-based product that contains acarbonate/bicarbonate mixture in a buffering effective amount willgenerally require a greater amount of acid for acidifying the fluid.Acidifying conditions may include, for example, a temperature in therange from 0° C. to 200° C.; or in the range from 10° C. to 150° C.; orin the range from 20° C. to 100° C.; or even in the range from 25° C. to75° C.

During pH titration, the non-ionized organic acids which are formed areless soluble in the aqueous mobile kerogen-based product than are theionized organic acids; these relatively insoluble organic acids form aseparate liquid phase from the kerogen-based product, and may beisolated from the product using conventional liquid-liquid separationmethods.

High molecular weight organic acids, including kerogen fragments thatform either an emulsion or a solution in highly alkaline aqueous fluids,may be separated from the aqueous fluids at pH values of at least 7.Under these conditions, gaseous CO2 that is provided to the mobilekerogen-based product is adequate for reducing the pH such that thesehigh molecular weight organic acids separate from the mobilekerogen-based product as a separate liquid, or solid, phase. In oneembodiment, at least a portion of the gaseous CO₂ used for pH titrationis recovered from a decarboxylation process or from the pH titrationprocess.

In one embodiment, the process of isolating organic acids is modified tofacilitate the separation of product organic acids. Fractionalneutralization is an example of such a process. During fractionalneutralization, the mobile kerogen-based product is treated insequential steps; the treatment process converts increasingly largeramounts of relatively more soluble ionized organic acids to relativelymore insoluble non-ionized organic acids. The organic acids which areisolated during each stage of the fractional neutralization process arecharacterized by a particular set of chemical and physical properties,such as molecular weight, number of carboxylate groups per molecule, andthe olefinicity of the organic acids. In an illustrative example of afractional neutralization process, a mobile kerogen-based product istreated with an acid to reduce the pH of the mobile kerogen-basedproduct to a target value. Dissolved reaction products that arerelatively insoluble in aqueous fluid at that pH form a separate phase,at least a portion of which is isolated from the remaining mobilekerogen-based product. Two phase separation methods are known. In oneembodiment, the separation is facilitated by adding an organicextraction fluid, before, during or after acidification, for extractingthe relatively insoluble products from the aqueous mobile kerogen-basedproduct. After recovery of the separate organic acid phase, the mobilekerogen-based product is further acidified to progressively lower pHvalues, and the separate organic acid liquid phase that is produced witheach step of acidification is recovered, optionally with the use ofadditional amounts of one or more organic extraction fluids.

When carbonate or bicarbonate containing materials are present in theformation fluid, increasing the amount of added acid will also generallyincrease the amount of evolved carbon dioxide. In some situations, thegenerated carbon dioxide is captured and used, for example, formanufacturing and commercial applications, for enhancing the recovery ofhydrocarbons from subsurface reservoirs, or disposed, for example insubsurface cavities, to reduce carbon dioxide emissions into theatmosphere.

In one embodiment, separation of the organic acids from an aqueousmobile kerogen-based product is facilitated by contacting the productwith an organic extraction fluid, which is selected to be relativelyinsoluble in the aqueous fluid, to have a high solubility for organicacids, to have adequate chemical stability at the conditions of theextraction and to be relatively easily separated from the organic acidsin a subsequent separation step. Contacting the product with the organicextraction fluid produces a two phase liquid system, in which at least aportion of the acids in the aqueous product is extracted into theorganic extraction fluid to form an acid rich extraction fluid, which isthen recovered. The organic extraction fluid may be selected topreferentially partition a certain group of organic acids, so as toseparate the organic acid product into groups by one or more desiredphysical and/or chemical property. The organic acids are separated fromthe organic extraction fluid using known separation methods, includingdistillation.

Typical organic extraction fluids include C₄ to C₂₁ hydrocarbons,including naphtha, diesel fuel, and gas oils; alcohols, includingmethanol, ethanol, propanol, butanol; aromatics, including benzene,toluene, the xylenes and alkyl substituted variations thereof; ethers;ketones; esters; tetralin; n-methyl-2-pyrrolidone; tetrahydrofuran;2-methyl tetrahydrofurane.

Extraction conditions are generally mild, including a temperature, forexample in the range from 0° C. to 200° C.; or in the range from 10° C.to 150° C.; or in the range from 20° C. to 100° C.; or even in the rangefrom 25° C. to 75° C.

In general, an organic extraction fluid is use in the process isrecycled to the process. In one embodiment, the process comprisesextracting at least a portion of the organic acids into a first organicextraction fluid to form an acid rich extraction fluid; isolating atleast a portion of the organic acids from the acid rich extractionfluid, and forming a second organic extraction fluid; and recycling thesecond organic extraction fluid to the extraction step.

Organic acids may be isolated from the mobile kerogen-based productusing esterification. In general, the esters that are formed are lesssoluble in an aqueous fluid than are the organic acids. Insoluble estersare separated from the aqueous fluid by liquid-liquid separationtechniques.

Products

It may be desirable to recover the organic acids from the mobilekerogen-based product as a syncrude which contains at least a portion ofthe organic acids that are insoluble in aqueous fluid at a pH of lessthan 2.0 or at a pH of less than 1.5. The syncrude prepared in this waywill include organic acids of C₁₂ and higher, with deceasing amounts oforganic acids of carbon number below C₁₂, depending on the particularacids. In one embodiment, the syncrude will include organic acids in therange of C₁₂ to C₃₅; or C₁₂ to C₃₀; or C₁₂ to C₂₀. Syncrude is asuitable feedstock for refining, petrochemical and power generatingfacilities.

The kerogen fragments that are recovered from the mobile kerogen-basedproduct are generally very high molecular weight molecular clusters withsufficient numbers of acid functions to be mobilized in aqueous ororganic solution. These kerogen fragments have a lower molecular massthan the naturally occurring kerogen itself, and with the characteristicchemical and conformational complexity of the kerogen structures fromwhich they are derived. In one embodiment, the kerogen fragments areC₃₅+ organic acids. In one embodiment, the kerogen fragments have amolecular weight of greater than 1000 daltons. In one embodiment, atleast a portion of the kerogen fragments have a molecular mass of up to12,000 to 15,000 Daltons. In one embodiment, at least a portion of thekerogen fragments have a molecular mass of greater than 15,000 daltons.

The C₁₀ to C₃₅ organic acids are important for preparing fuels andlubricants, petrochemicals and petrochemical feedstocks, refinery rawmaterials and process oils. Many specialized products have been proposedfor organic acids in this molecular weight range. For example, refineryprocesses such as hydroprocessing, hydrogenation, saturation,hydrotreating, hydrocracking, isomerization, fluid catalytic cracking,thermal cracking, esterification, oligomerization, reforming,alkylation, denitrification and desulfurization are suitable forupgrading the organic acids to commercially valuable products.

In some situations, it may be desirable to leave a relatively smallamount of acids in the treated fluid produced after the organic acidsare removed from the mobile kerogen-based product after acidificationand organic acid recovery. For example, the treated formation fluid fromthe isolation step contains low amounts of organic acids and otherorganic molecules, which may provide surfactant properties to thetreated formation fluid. The treated fluid containing low amounts oforganic acids and other organic molecules is referenced herein as anorganic acid lean fluid and is typically aqueous. In one embodiment, theorganic acid lean fluid comprises C₂ to C₁₀ organic acids. In anembodiment, the organic acid lean fluid comprises organic acids in therange of from 0.001 wt % to 10 wt %.

The treated aqueous may be recycled, for example, for additionalreaction and/or extraction and recovery of mobile kerogen-based productsfrom the subsurface shale formation. As such, the process is integratedand uses a product stream in creating additional mobile kerogen-basedproducts. This integration creates additional efficiencies in theprocess, creating more desired products and using a broader range of theproducts created.

As such, in one embodiment an integrated process for extractingkerogen-based products from a subsurface shale formation comprisingkerogen in an inorganic matrix is provided. This integrated processcomprises providing an oxidant to the kerogen in the subsurface shaleformation; contacting the kerogen in the subsurface shale formation withthe oxidant at a temperature in the range from 0° C. and 200° C. to formorganic acids; mobilizing at least a portion of the organic acids asorganic acid reaction products from the subsurface shale to produce amobile kerogen-based product; treating the mobile kerogen-based productto provide a product stream comprising C₁₂ and higher organic acids andan organic acid lean fluid comprising C₂ to C₁₀ organic acids; andrecycling the organic acid lean fluid to the subsurface shale formation.

Depending on the processing used to isolate organic acids from themobile kerogen-based product, the organic acid lean fluid may range inpH from 2 or less to above 8.5. This organic acid lean fluid may bemodified and prepared for recycling with an added oxidant as a reactivefluid to the kerogen in the subsurface shale. When used as a recyclereactive fluid, oxidant is added to the organic acid lean fluid and thenrecycled to the subsurface shale formation. The oxidant can be added inan amount of from 0.1 wt % to 40 wt %. The pH of the organic acid leanfluid can be tailored to the effective range for the particular oxidantor oxidant mixture. Additional surfactant may also be added as required.If necessary to achieve the target pH, an alkaline material can be addedto the organic acid lean fluid prior to recycling.

The organic acid lean fluid may also be prepared for recycling as anextractive fluid. As such, the organic acid aqueous fluid can beisolated and recycled to the subsurface shale formation for mobilizingat least a portion of the organic acids as organic acid reactionproducts to produce a mobile kerogen-based product. When used as recycleextractive fluid, the pH of the organic acid lean fluid can be tailoredto the effective range for mobilizing at least a portion of the organicacids as organic acid reaction products. If necessary to achieve thetarget pH, an alkaline material can be added to the organic acid leanfluid prior to recycling. Additional surfactant may also be added asrequired.

One embodiment of the process includes providing an oxidant to thekerogen in the subsurface shale formation; contacting the kerogen in thesubsurface shale formation with the oxidant at a temperature in therange of between 0° C. and 200° C. to form organic acids; mobilizing atleast a portion of the organic acids as organic acid reaction productsfrom the subsurface shale formation to produce a mobile kerogen-basedproduct; treating the mobile kerogen-based product to provide a productstream comprising C₁₂ and higher organic acids and an organic acid leanfluid comprising C₂ to C₁₀ organic acids; combining the organic acidaqueous fluid with an oxidant to provide a recycling fluid; andrecycling the recycle fluid to the subsurface shale formation andcontacting the kerogen in the subsurface shale formation with theoxidant in the recycle fluid for additional oxidation and formation oforganic acids.

Another embodiment of the process includes providing an oxidant to thekerogen in the subsurface shale formation; contacting the kerogen in thesubsurface shale formation with the oxidant at a temperature in therange of between 0° C. and 200° C. to form organic acids; mobilizing atleast a portion of the organic acids as organic acid reaction productsfrom the subsurface shale formation to produce a mobile kerogen-basedproduct; treating the mobile kerogen-based product to provide a productstream comprising C₁₂ and higher organic acids and an organic acid leanfluid comprising C₂ to C₁₀ organic acids; isolating the organic acidaqueous fluid as a recycling fluid; and recycling the recycle fluid tothe subsurface shale formation and mobilizing at least a portion of theorganic acids as organic acid reaction products to produce a mobilekerogen-based product.

The organic acid lean fluid can also be separated into two portions withone portion being used as additional reactive fluid with added oxidantand one portion being used as extractive fluid to assist in mobilizingat least a portion of the organic acids as organic acid reactionproducts to produce a mobile kerogen-based product.

Upgrading

As described, organic acids and other kerogen reaction products areseparated from the mobile kerogen-based product. In further embodiments,the extracted kerogen-based product is upgraded to yield one or morecommercial petroleum-based products. Various techniques common in theindustry (e.g., hydroprocessing, hydrogenation, saturation,hydrotreating, hydrocracking, isomerization, fluid catalytic cracking,thermal cracking, esterification, oligomerization, reforming,alkylation, denitrification and desulfurization) may be employed toobtain a desired commercial product from the extracted kerogen-basedproduct. Such upgrading is largely dependent on the nature of theextracted kerogen-based product relative to the commercial product thatis desired.

The organic acids are used, for example, in the production of fuels,lubricant and lubricant base oils, polymers, pharmaceuticals, solvents,petrochemicals and food additives. In one embodiment, the acids areseparated by e.g., chemical type or boiling range for specific chemicaland petrochemical applications, including feedstock and end useapplications. In one embodiment, at least some of the acids are used asfeedstocks to make lubricating oil base stocks having a viscositygreater than or equal to 3 cSt at 40° C.; a pour point at or below 20°C., or at or below 0° C.; and a VI at least 70, or at least 90, or atleast 120. It is optionally used with additives, and/or other base oils,to make a finished lubricant. The finished lubricants can be used inpassenger car motor oils, industrial oils, and other applications. Whenused for passenger car motor oils, base oils meet the definitions of thecurrent version of API Base Oil Interchange Guidelines 1509.

In general, C₂₀− organic acids find particular use in the production offuels, lubricant and lubricant base oils, polymers, pharmaceuticals,solvents, petrochemicals and food additives. Therefore, in oneembodiment, a method for increasing the value of a kerogen-based productincludes isolating C₂₀+ organic acids and C₂₀− organic acids from themobile kerogen-based product, and converting at least a portion of theC₂₀+ organic acids to C₂₀− organic acids. The separation step mayinclude a process selected from the group consisting of pH titration,fractional neutralization, esterification, extraction, distillation,membrane separation, froth flotation, phase separation, electrostaticseparation, filtering, centrifugal separation, coalescence,precipitation, thermal separation, steam distillation, and anycombination thereof, in any order. In one embodiment, the mobilekerogen-based product from which the C₂₀+ and C₂₀− organic acids areisolated is treated at a pH in the range from 1.5 to 7 to achieve theseparation. In one embodiment, the C₂₀+ organic acids are cracked in aprocess that converts at least a portion of the C₂₀+ organic acids toC₂₀− hydrocarbon products. In one embodiment, unconverted C₂₀+ organicacids are recycled to the cracking process, until virtually all of theC₂₀+ organic acids are reduced to C₂₀− forms. Exemplary crackingreactions include pyrolysis, partial oxidation, and fluid catalyticcracking and hydrocracking. In one embodiment, partial oxidation isconducted in the presence of an oxidant. In one embodiment, the C₂₀−hydrocarbon product is upgraded, using a process selected from the groupconsisting of hydroprocessing, hydrogenation, saturation, hydrotreating,hydrocracking, isomerization, fluid catalytic cracking, thermalcracking, esterification, oligomerization, reforming, alkylation,denitrification, desulfurization, and combinations thereof. In anotherembodiment, a blend of the C₂₀− hydrocarbon product and the C₂₀− organicacids are blended, and the blend is upgrading, using a process selectedfrom the group consisting of hydroprocessing, hydrogenation, saturation,hydrotreating, hydrocracking, isomerization, fluid catalytic cracking,thermal cracking, esterification, oligomerization, reforming,alkylation, denitrification, desulfurization, and combinations thereof.In one embodiment, the upgraded products are useful as a refineryfeedstock, a fuel or lubricant blendstock, a reaction intermediate, achemical feedstock, or a chemical intermediate blendstock.

In one embodiment, at least a portion of the organic acids in the mobilekerogen-based product are solid organic acids. Some of the solid, highmolecular weight organic acids are difficult to dissolve in a solvent orto melt without decomposing. Accordingly, in one embodiment, the C₃₅+organic acids that are isolated from the mobile kerogen-based product iscracked prior to downstream upgrading processes. In one such embodiment,the cracking process is selected from the group consisting of pyrolysis,partial oxidation, fluid catalytic cracking and hydrocracking. The C₃₅−hydrocarbon products from the cracking reaction are further upgraded ina process selected from the group consisting of hydroprocessing,hydrogenation, saturation, hydrotreating, hydrocracking, isomerization,fluid catalytic cracking, thermal cracking, esterification,oligomerization, reforming, alkylation, denitrification,desulfurization, and combinations thereof. In one embodiment, the atleast a portion of the C₃₅− hydrocarbon products are blended with atleast a portion of the C₃₅− organic acids, and the blend upgraded in aprocess selected from the group consisting of hydroprocessing,hydrogenation, saturation, hydrotreating, hydrocracking, isomerization,fluid catalytic cracking, thermal cracking, esterification,oligomerization, reforming, alkylation, denitrification,desulfurization, and combinations thereof. In one embodiment, theupgraded products are useful as a refinery feedstock, a fuel orlubricant blendstock, a reaction intermediate, a chemical feedstock, ora chemical intermediate blendstock.

In one such embodiment, the process includes pyrolyzing the solidorganic acids to form C₂₀− hydrocarbon products and C₂₀+ products;recovering the C₂₀+ products; and pyrolyzing the C₂₀+ products. Inanother such embodiment, the process includes pyrolyzing the solidorganic acids to form C₃₅− hydrocarbon products and C₃₅+ products;recovering the C₃₅+ products; and pyrolyzing the C₃₅+ products.

In one embodiment, at least some of the acids are used as feedstocks tomake distillate fuels, generally boiling in the range of about C5-700°F. (121°-371° C.) as determine by the appropriate ASTM test procedure.The term “distillate fuel” is intended to include gasoline, diesel, jetfuel and kerosene boiling range fractions. The kerosene or jet fuelboiling point range is intended to refer to a temperature range of about280°-525° F. (138°-274° C.) and the term “diesel boiling range” isintended to refer to hydrocarbon boiling points of about 250°-700° F.(121°-371° C.). Gasoline or naphtha is normally the C₅ to 400° F. (204°C.) endpoint fraction of available hydrocarbons. The boiling pointranges of the various product fractions reco_(ve)red in any particularrefinery or synthesis process will vary with such factors as thecharacteristics of the source, local markets, product prices, etc.Reference is made to ASTM standards D-975, D-3699-83 and D-3735 forfurther details on kerosene, diesel and naphtha fuel properties.

In one embodiment, the organic acids are upgraded in a hydrotreatingreaction zone to rem_(ov)e heteroatoms such as oxygen, nitrogen andsulfur and to saturate olefins and aromatics. Hydrotreating conditionsinclude a reaction temperature between 400° F.-900° F. (204° C.-482°C.), or between 650° F.-850° F. (343° C.-454° C.); a pressure between500 to 5000 psig (pounds per square inch gauge) (3.5-34.6 MPa), orbetween 1000 to 3000 psig (7.0-20.8 MPa); a feed rate (LHSV) of 0.5 hr-1to 20 hr-1 (v/v); and overall hydrogen consumption 300 to 2000 scf perbarrel of liquid hydrocarbon feed (53.4-356 m3 H2/m3 feed). Thehydrotreating catalyst will generally be a composite of a Group VI metalor compound thereof, and a Group VIII metal or compound thereofsupported on a porous refractory base such as alumina. Examples ofhydrotreating catalysts are alumina supported cobalt-molybdenum, nickelsulfide, nickel-tungsten, cobalt-tungsten and nickel-molybdenum. Otherexamples of hydrotreating catalysts contain a platinum group metal suchas platinum and/or palladium. Typically such hydrotreating catalysts arepresulfided.

In one embodiment, the organic acids or reaction products derived fromthe organic acids are hydrocracked. The hydrocracking reaction zone ismaintained at conditions sufficient to effect a boiling range conversionof the organic acids or derivatives thereof to the hydrocrackingreaction zone, so that the liquid hydrocrackate recovered from thehydrocracking reaction zone has a normal boiling point range below theboiling point range of the feed. The hydrocracking step reduces the sizeof the hydrocarbon molecules, hydrogenates olefin bonds, hydrogenatesaromatics, and removes traces of heteroatoms resulting in an improvementin fuel or base oil product quality.

Typical hydrocracking conditions include a reaction temperature between400° F. and 950° F. (204° C.-510° C.) or between 650° F. and 850° F.(343° C.-454° C.); a reaction pressure between 500 and 5000 psig(3.5-34.5 MPa) or between 1500 and 3500 psig (10.4-24.2 MPa); a feedrate (in terms of volumes of feed at ambient conditions per volume ofcatalyst per hour) between 0.1 and 15 hr-1 (v/v) or between 0.25 and 2.5hr-1; and hydrogen consumption 500 to 2500 scf per barrel of liquidhydrocarbon feed (89.1-445 m3 H2/m3 feed). Generally, more severeconditions within these ranges will be used with higher boilingfeedstocks and depending on whether gasoline, middle distillate orlubricating oil is desired as the primary economic product. Thehydrocrackate is then separated into various boiling range fractions.The separation is typically conducted by fractional distillationpreceded by one or more vapor-liquid separators to remove hydrogenand/or other tail gases.

The hydrocracking catalyst generally comprises a cracking component, ahydrogenation component and a binder. Such catalysts are well known inthe art. The cracking component may include an amorphous silica/aluminaphase and/or a zeolite, such as a Y-type or USY zeolite. The binder isgenerally silica or alumina. The hydrogenation component will be a GroupVI, Group VII, or Group VIII metal or oxides or sulfides thereof,preferably one or more of molybdenum, tungsten, cobalt, or nickel, orthe sulfides or oxides thereof. If present in the catalyst, thesehydrogenation components generally make up from about 5% to about 40 wt.% of the catalyst. Alternatively, platinum group metals, especiallyplatinum and/or palladium, may be present as the hydrogenationcomponent, either alone or in combination with the base metalhydrogenation components molybdenum, tungsten, cobalt, or nickel. Ifpresent, the platinum group metals will generally make up from about0.1% to about 2 wt. % of the catalyst.

In one embodiment, the organic acids or reaction products derived fromthe organic acids are hydroisomerized. Typical hydroisomerizationconditions are well known in the literature and can vary widely.Isomerization processes are typically carried out at a temperaturebetween 200° F. and 700° F. or between 300° F. to 650° F., with a feedrate between 0.1 and 10 hr-1 or between 0.25 and 5 hr-1. Hydrogen isemployed such that the mole ratio of hydrogen to hydrocarbon is between1:1 and 15:1. Catalysts useful for isomerization processes are generallybifunctional catalysts that include a dehydrogenation/hydrogenationcomponent and an acidic component. The acidic component may include oneor more of amorphous oxides such as alumina, silica or silica-alumina; azeolitic material such as zeolite Y, ultrastable Y, SSZ-32, Betazeolite, mordenite, ZSM-5 and the like, or a non-zeolitic molecularsieve such as SAPO-11, SAPO-31 and SAPO-41. The acidic component mayfurther include a halogen component, such as fluorine. The hydrogenationcomponent may be selected from the Group VIII noble metals such asplatinum and/or palladium, from the Group VIII non-noble metals such asnickel and tungsten, and from the Group VI metals such as cobalt andmolybdenum. If present, the platinum group metals will generally make upfrom about 0.1% to about 2 wt. % of the catalyst. If present in thecatalyst, the non-noble metal hydrogenation components generally make upfrom about 5% to about 40 wt. % of the catalyst.

In one embodiment, the organic acids or reaction products derived fromthe organic acids are cracked in a fluid catalytic cracking unit (FCC).In such fluidized catalytic cracking, high molecular weight hydrocarbonliquids and vapors are contacted with hot, finely divided solid catalystparticles in an elongated riser or transfer line reactor. The transferline is usually in the form of a riser tube and the contacting time ison the order of a few seconds, say from 0.5 to 8 seconds, and generallynot over about 4 seconds. During this short period, catalysts attemperatures in the range about 1100° F. to 1400° F. are contacted witha hydrocarbon feedstock which is heated to a temperature of about 300°F. to 800° F. The reaction is one of essentially instantaneousgeneration of large volumes of gaseous hydrocarbons. The hydrocarbonsand catalyst mixture flows out of the riser tube into a reactor vesselwherein the resultant gaseous hydrocarbons are taken off fordistillation into various product fractions defined by boiling ranges.The spent catalyst is then separated in the reactor vessel and strippedof hydrocarbons by passing the catalyst through a stripper section whichincludes steam flowing up through the down-flowing catalyst usually fora period of 1 to 3 minutes. Catalyst is then returned to a regeneratorwhere residual hydrocarbons, called “coke”, on the spent catalyst areburned off by passing a stream of an oxygen-containing gas, such as air,or oxygen-enriched air, through the catalyst until substantially all thecarbon is burned from the particles. The heat generated in thisregeneration step is used as a heat source to heat the catalyst and thusprovide elevated temperatures needed for reaction with the incominghydrocarbon feed. Regenerated hot catalyst is then recycled to the risercracking zone wherein the feed is cracked to form more gaseous products.In one embodiment, the fluid catalytic cracking reaction of the organicacids is conducted at a temperature of between 1200° F. and 1400° F.(600° C. to 800° C.). In another embodiment the fluid catalytic crackingreaction of the organic acids is conducted at a temperature of between250° C. and 490° C.

A typical catalyst comprises 10%-60% w/w of a solid acid, 0%-50% w/w ofalumina, 0%-40% w/w of silica, the remainder being kaolin. The solidacid may be a zeolite of the ZSM type, a zeolite of the faujasite type,a zeolite of the mordenite type, silico-aluminum phosphate (SAPO) oraluminum phosphate (ALPO).

Many refineries operate a single reactor for fluid catalytic cracking ofgas oil or residue. In some situations, refineries may employ an FCCUpossessing two reactors working in simultaneous operation. In such unitsthe streams of spent catalyst from two reactors are mixed in the samerectification section having a single regenerator to burn off cokedeposited on the catalyst. In addition such reactors may function in anindependent manner with respectively different types of charge anddiffering reaction temperatures. The reaction severity applied to eachreactor may be totally different, making it possible to adjust them topreestablished operational objectives. In this manner it is possible tocarry out the processing of the organic acids under milder conditions,at temperatures between 250° C. and 490° C., for the production ofdiesel oil having a cetane number exceeding 40, while simultaneouslycarrying out the processing of conventional heavy gas oils or residuesunder more severe conditions, employing a single catalyst flow for bothprocesses.

The method of the present invention for converting the organic acids toesters involves blending suitable amounts of an alcohol, such asalcohol, and an acid catalyst with the organic acids. The reactionmixture is then subjected to conditions suitable for forming the esters.

A suitable amount of alcohol for the method of the present invention isan amount that is about 100% to about 470% of the theoretical amountneeded to convert all organic acids into esters. The theoretical amountof alcohol needed to convert all organic acids into esters is defined asan equal number of alcohol molecules as that of organic acid molecules.In one embodiment, an amount of alcohol about 120% to about 300% of thetheoretical amount is used in the method of the present invention. Inanother embodiment, an amount of alcohol between 100% and 150% of thetheoretical amount is used. In still another embodiment, an amount ofalcohol about 270% of the theoretical amount is used.

Suitable acid catalysts for converting organic acids to esters are knownin the art. Any of these catalysts can be used in the process. Examplesof these catalysts include but are not limited to sulfuric acid,hydrogen chloride and p-toluenesulfonic acid. When sulfuric acid isused, a suitable amount is about 0.1% to about 7.5% by weight in thereaction mixture. In one embodiment, the amount of sulfuric acid used isabout 0.6% to about 5.8% or about 1.2%. When other acid catalysts areused, a skilled artisan either knows or can easily determine thesuitable amount that can be added into the reaction mixture.

The speed that organic acids are converted to esters in the reactionmixtures described above is a function of the reaction temperature—thehigher the reaction temperature, the higher the speed. In oneembodiment, the reaction temperature used for esterifying the acids isat least 20° C.; or 25° C.; or 30° C.; or 35° C.; or 40° C.; or 45° C.with stirring. Most preferably, the reaction temperature is kept atabout at least 50° C.; or 55° C.; or 60° C.; or 65° C. In oneembodiment, the reaction temperature is the boiling point of the alcoholat the reaction pressure. The reaction pressure for esterification isgenerally equal to or slightly above (e.g., 200 psig) atmosphericpressure.

The reaction time needed to convert a desired percentage of organicacids into esters under specific amounts of alcohol, acid catalyst andreaction temperature can readily be determined by a skilled artisan. Forexample, a small sample of the reaction mixture can be taken atdifferent time points and the organic acid level and ester level can bedetermined. Generally speaking, the reaction time range goes from 0.5 hrto 2.0 hr; or to 3.0 hr; or to 5.0 hr; or to 10 hr.

FIG. 6 illustrates a specific embodiment of the process for isolatingand upgrading the organic acids derived from subsurface kerogen. In theprocess, a mobile kerogen-based product 206 is contacted with organicextraction fluid 202 and acid 204 in treating step 210 at a pH in therange from 7 to 12 to produce an acid rich extraction fluid 217 and C₃₅−organic acid containing mobile kerogen-based product 215. The acid richextraction fluid 217 is separated in step 240 into a recycle extractionfluid 247 and C₃₅+ organic acids 245. Recycle extraction fluid 247 isrecycled to fresh organic extraction fluid 202.

C₃₅− organic acid containing mobile kerogen-based product 215 iscontacted with organic extraction fluid 222 and acid 224 in treatingstep 220 at a pH in the range from 1.5 to 6.5 to produce an acid richextraction fluid 227 and C₁₀− organic acid containing mobilekerogen-based product 225. The acid rich extraction fluid 227 isseparated in step 250 into a recycle extraction fluid 257 and C₁₂-C₃₅organic acids 255. Recycle extraction fluid 257 is recycled to freshorganic extraction fluid 222.

C₁₀− organic acid containing mobile kerogen-based product 225 is furtherprocessed in treating step 230 to yield C₂-C₁₀ organic acids 235 andorganic acid lean aqueous fluid 237.

In the upgrading portion of the process, C₃₅+ organic acids 245 arepassed to cracking reactor 260. Unreacted acids 265 are recycled to 245,and C₃₅− hydrocarbon products 267 are passed to product upgrader 270,along with C₁₂-C₃₅ organic acids 255. The blend is upgraded in 270. Theproduct 275 is useful as a refinery feedstock, a fuel or lubricantblendstock, a reaction intermediate, a chemical feedstock, or a chemicalintermediate blendstock.

EXAMPLE

This example illustrates the effectiveness of potassium permanganate forproducing high molecular weight organic acids in reactions with kerogen.

Kerogen was separated from a sample of oil shale that contained kerogen.The separated kerogen was largely organic matter, with a small amount ofinorganic matter remaining from the inorganic substrate in which thekerogen originated. For this example, 2.50 grams of kerogen (organicmatter basis) was combined with a solution containing 0.5 g KMnO4 in 100ml of 1% KOH solution. The kerogen/KMnO4 mixture was stirred at 75° C.until the solution had lost its color, with no visual evidence of thepurple permanganate color remaining. In general, this reaction tookseveral hours, and up to 12 hours in some cases. The kerogen was thenallowed to settle, and was separated from the solution. The kerogen wasthen rinsed with two 75 ml aliquots of 1% KOH solution. The two rinsesolutions were set aside. The rinsed kerogen was then contacted withanother aliquot of KMnO₄ solution, and the oxidation and washing stepswere repeated. After five successive KMnO₄ treatments, the kerogen waswashed with oxalic acid solution at low pH to dissolve MnO₂ which wasdeposited on the kerogen surface. The kerogen was then rinsed before thenext KMnO₄ treatment step. At the end of 17 KMnO₄ treatments, thekerogen was effectively consumed, and the permanganate color of thesolution no longer disappeared. All of the 1% KOH rinse solutionscollected from each treatment step were combined and acidified to pH 2.High molecular weight acids in the acidified solution precipitated fromsolution and were recovered. Low molecular weight acids in the solutionwere extracted with methyl t-butyl ether and recovered by removing theether solvent.

FIG. 4 illustrates the gas chromatographic separation of the lowmolecular weight acids. A high proportion of the low molecular weight(i.e., C₃₅−) organic acids are in the C₈ to C₁₂ range. In particular,FIG. 4 shows carbon chain-size distribution of low molecular weightorganic acids (di-carboxylic acids and mono-carboxylic acids) in kerogenpermanganate oxidation products determined by gas chromatography—massspectrometry (GCMS) of their silyl derivatives. The high-pH aqueousreaction product solution was adjusted to ˜pH 2 and extracted withmethyl t-butyl ether solvent to yield low molecular weight organic acidsupon solvent removal. GCMS analysis showed these organic acids containprimarily straight (un-branched) alkyl chains. Hydroprocessing of thislow molecular weight organic acids product to remove oxygen and otherheteroatoms would provide the alkane mixture shown in the figure, wherethe number of carbon atoms in each of the major, straight-chain productpeaks is labeled. The carbon number distribution of products range from˜C₆ to ˜C₁₇ (with a maximum at C₉), covering the highly desirablegasoline, jet, and diesel transportation fuel hydrocarbon molecularweight range.

The high molecular weight (i.e., C₃₅+) organic acids were passed througha pyrolysis gas chromatograph, which thermally pyrolyzed the acids. FIG.5 is a gas chromatographic trace of the pyrolyzed acids. In particular,FIG. 5 shows carbon chain-size distribution of hydrocarbon productsformed by pyrolysis of high molecular weight organic acids in kerogenpermanganate oxidation products determined by pyrolysis gaschromatography—mass spectrometry (pyrolysis-GCMS). The high-pH aqueousreaction product solution was adjusted to ˜pH 2 resulting in theprecipitation of high molecular weight organic acids which werecollected, washed with deionized water, and dried under vacuum.Pyrolysis-GCMS analysis showed these high molecular weight organic acidsto yield primarily straight (un-branched) alkanes and alkenes uponheating to 500° C. in inert atmosphere. The number of carbon atoms ineach of the major, straight-chain product peaks is labeled in thefigure—each carbon number labels two peaks, consisting of an alkane andalkene pair, typical of pyrolysis/retort products. Hydroprocessing ofthe pyrolysis (retort) products shown in the figure, to remove alkenesand heteroatoms, would provide an alkane mixture with a carbon numberdistribution ranging from ˜C₅ to ˜C₃₁ (with a maximum at C₉), coveringthe highly desirable gasoline, jet, and diesel fuel hydrocarbonmolecular weight range, with a small proportion of product in the fueloil and lube oil hydrocarbon molecular weight range.

It is interesting to note that the profile of the pyrolyzed acids isvery similar to the profile of the low molecular weight acids. Inparticular, a high proportion of the pyrolyzed organic acids are also inthe C₈ to C₁₂ range.

A variation (i.e., alternate embodiment) on the above-described processis the application of some or part of such above-described methods toalternative sources, i.e., low-permeability hydrocarbon-bearing (e.g.,oil and gas) formations, in situ coal, in situ heavy oil, in situ oilsands, and the like. General applicability of at least some of theabove-described invention embodiments to any hydrocarbon-bearingformation exists. Surface processing applications may include upgradingof oil shale, coal, heavy oil, oil sands, and other conventional oilswith asphaltenes, sulfur, nitrogen, etc.

Various modifications and alterations of this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of the invention. Other objects and advantages will becomeapparent to those skilled in the art from a review of the precedingdescription.

What is claimed is:
 1. A process for increasing the value of akerogen-based product from a subsurface shale formation comprisingsubsurface shale, the process comprising the steps of: a. providing anoxidant to kerogen in subsurface shale at a temperature in the rangefrom 0° C. to 200° C. and recovering a mobile kerogen-based productcomprising organic acids therefrom; b. isolating at least a portion ofthe organic acids from the mobile kerogen-based product; and c.upgrading the isolated organic acids.
 2. The process according to claim1, wherein providing an oxidant to kerogen in subsurface shale furthercomprises: a. contacting kerogen in subsurface shale with an oxidant ata temperature in the range from 0° C. to 200° C. to form organic acids;and b. mobilizing at least a portion of the organic acids from thesubsurface shale to produce a mobile kerogen-based product.
 3. Theprocess according to claim 1, further comprising isolating at least aportion of the organic acids from the mobile kerogen-based product byemploying an process selected from the group consisting of pH titration,fractional neutralization, esterification, extraction, distillation,membrane separation, froth flotation, phase separation, electrostaticseparation, filtering, centrifugal separation, coalescence,precipitation, thermal separation, steam distillation, and anycombination thereof, in any order.
 4. The process according to claim 1,wherein upgrading the isolated organic acids further comprises isolatingC₂₀+ organic acids and C₂₀− organic acids from the mobile kerogen-basedproduct, and cracking at least a portion of the C₂₀+ organic acids in acracking process.
 5. The process according to claim 4, furthercomprising cracking at least a portion of the C₂₀+ organic acids in aprocess selected from the group consisting of pyrolysis, partialoxidation, fluid catalytic cracking and hydrocracking.
 6. The processaccording to claim 4, further comprising cracking at least a portion ofthe C₂₀+ organic acids in a cracking process, recovering at least a C₂₀−hydrocarbon product and C₂₀+ organic acids, and recycling at least aportion of the C₂₀+ organic acids to the cracking process.
 7. Theprocess according to claim 6, further comprising upgrading the C₂₀−hydrocarbon product in a process selected from the group consistinghydroprocessing, hydrogenation, saturation, hydrotreating,hydrocracking, isomerization, fluid catalytic cracking, thermalcracking, esterification, oligomerization, reforming, alkylation,denitrification, desulfurization, and combinations thereof.
 8. Theprocess according to claim 7, further comprising using at least aportion of the upgraded C₂₀− hydrocarbon product as a blendstock for afuel or a lubricating oil base stock.
 9. The process according to claim6, further comprising blending at least a portion of the C₂₀−hydrocarbon product and at least a portion of the C₂₀− organic acids andupgrading the blend in a process selected from the group consisting ofhydroprocessing, hydrogenation, saturation, hydrotreating,hydrocracking, isomerization, fluid catalytic cracking, thermalcracking, esterification, oligomerization, reforming, alkylation,denitrification, desulfurization, and combinations thereof.
 10. Theprocess according to claim 9, further comprising using at least aportion of the upgraded C₂₀− hydrocarbon product as a blendstock for afuel or lubricating oil base stock.
 11. The process according to claim1, wherein upgrading the isolated organic acids further comprisesisolating C₃₅+ organic acids and C₃₅− organic acids from the mobilekerogen-based product, and cracking at least a portion of the C₃₅+organic acids in a cracking process.
 12. The process according to claim11, further comprising cracking at least a portion of the C₃₅+ organicacids in a process selected from the group consisting of pyrolysis,partial oxidation, fluid catalytic cracking and hydrocracking.
 13. Theprocess according to claim 11, further comprising cracking at least aportion of the C₃₅+ organic acids in a cracking process, recovering atleast a C₃₅− hydrocarbon product and C₃₅+ organic acids, and recyclingat least a portion of the C₃₅+ organic acids to the cracking process.14. The process according to claim 13, further comprising upgrading theC₃₅− hydrocarbon product in a process selected from the group consistingof hydroprocessing, hydrogenation, saturation, hydrotreating,hydrocracking, isomerization, fluid catalytic cracking, thermalcracking, esterification, oligomerization, reforming, alkylation,denitrification, desulfurization, and combinations thereof.
 15. Theprocess according to claim 14, further comprising using at least aportion of the upgraded C₃₅− hydrocarbon product as a refineryfeedstock, a fuel or lubricant blendstock, a reaction intermediate, achemical feedstock, or a chemical intermediate blendstock.
 16. Theprocess according to claim 13, further comprising blending at least aportion of the C₃₅− hydrocarbon product and at least a portion of theC₃₅− organic acids and upgrading the blend in a process selected fromthe group consisting of hydroprocessing, hydrogenation, saturation,hydrotreating, hydrocracking, isomerization, fluid catalytic cracking,thermal cracking, esterification, oligomerization, reforming,alkylation, denitrification, desulfurization, and combinations thereof.17. The process according to claim 16, further comprising using at leasta portion of the upgraded C₃₅− hydrocarbon product as a refineryfeedstock, a fuel or lubricant blendstock, a reaction intermediate, achemical feedstock, or a chemical intermediate blendstock.
 18. Theprocess according to claim 1, wherein at least 50 wt. % of the organicacids in the mobile kerogen-based product are in the C₃₅+ range.
 19. Theprocess according to claim 1, wherein at least 20 wt. % of the C₃₅+organic acids in the mobile kerogen-based product have a molecular massnumber of greater than 1000 daltons.
 20. The process according to claim1, wherein at least 20 wt. % of the C₃₅− organic acids in the mobilekerogen-based product are in the C₈ to C₁₂ range.
 21. The processaccording to claim 1, wherein at least 30 wt. % of the organic acids inthe mobile kerogen-based product are diacids.
 22. A process forincreasing the value of a kerogen-based product from a subsurface shaleformation comprising subsurface shale, the process comprising the stepsof: a. providing an oxidant to kerogen in subsurface shale; b.contacting the kerogen in the subsurface shale with the oxidant at atemperature in the range of between 0° C. and 200° C. to form organicacids; c. mobilizing at least a portion of the organic acids from thesubsurface shale to produce a mobile kerogen-based product; d. isolatingC₃₅+ organic acids and C₃₅− organic acids from the mobile kerogen-basedproduct; e. cracking the C₃₅+ organic acids in a first cracking step toform a first C₃₅− hydrocarbon product and unreacted C₃₅+ organic acids;f. treating the first C₃₅− hydrocarbon product in a process selectedfrom the group consisting of hydroprocessing, hydrogenation, saturation,hydrotreating, hydrocracking, isomerization, fluid catalytic cracking,thermal cracking, esterification, oligomerization, reforming,alkylation, denitrification, desulfurization, and combinations thereof,to form a second C₃₅− hydrocarbon product; and g. recycling theunreacted C₃₅+ organic acids to the first cracking step.
 23. The processaccording to claim 22, wherein the first cracking step is selected fromthe group consisting of pyrolysis, partial oxidation, and fluidcatalytic cracking and hydrocracking.
 24. The process according to claim22, further comprising treating a combination of the first C₃₅−hydrocarbon product and the C₃₅− organic acids in a process selectedfrom the group consisting of hydroprocessing, hydrogenation, saturation,hydrotreating, hydrocracking, isomerization, fluid catalytic cracking,thermal cracking, esterification, oligomerization, reforming,alkylation, denitrification, desulfurization, and combinations thereof,to form a third C₃₅− hydrocarbon product.
 25. The process according toclaim 22, further comprising blending the first C₃₅− hydrocarbon productwith the second C₃₅− hydrocarbon product to make a fourth C₃₅−hydrocarbon product.